Organocatalytic Enantioselective Selenosulfonylation of a C–C

May 22, 2019 - ... was performed on an Agilent SuperNova-CCD X-ray diffractometer. ...... Asymmetry 2014, 25, 1561– 1572, DOI: 10.1016/j.tetasy.2014...
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Article Cite This: J. Org. Chem. 2019, 84, 8100−8111

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Organocatalytic Enantioselective Selenosulfonylation of a C−C Double Bond To Form Two Stereogenic Centers in an Aqueous Medium Zhili Chen,† Fangli Hu,† Shengli Huang,†,‡ Zhengxing Zhao,† Hui Mao,*,§ and Wenling Qin*,† Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, School of Pharmaceutical Sciences, and ‡School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, P. R. China § Pharmaceutical and Material Engineering School, Jinhua Polytechnic, Jinhua, Zhejiang Province 321000, P. R. China Downloaded via UNIV OF SOUTHERN INDIANA on July 17, 2019 at 16:37:56 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

†

S Supporting Information *

ABSTRACT: Organocatalytic selenosulfonylation of the C−C double bond of α,β-unsaturated ketones to construct two contiguous stereogenic centers in an aqueous medium was described. A series of α-selenyl and β-sulfonyl ketones with various functional groups were synthesized in good yields and enantioselectivities with saturated NaCl solution as the solvent. In addition, this protocol had been successfully scaled up to a decagram scale via a simple workup procedure.

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INTRODUCTION Both selenyl1 and sulfonyl2 groups are important functional groups in some biologically active molecules and functional organic materials. Selenium3 and sulfone4 can be readily transformed into useful building blocks, which constitute a family of synthetically valuable synthons. Therefore, the incorporation of selenium and sulfone into one molecular structure is of the significant synthetic value. Selenosulfonates were first reported by Foss in 19475 and provided a straightforward avenue to install selenium and sulfone groups in a single step through direct selenosulfonylation of an unsaturated substrate. As shown in Scheme 1a, Back and Collins reported the selenosulfonylation reaction of a variety of olefins to produce β-phenylseleno sulfones in the presence of boron trifluoride or elevated temperature in its absence.6 In addition, Kice demonstrated the photodecomposition of selenosulfonates and reported its addition to alkene to form βphenylseleno sulfones in good yield (Scheme 1a).7 In 1988, Backvall explored regioselective selenosulfonylation of the terminal C−C double bond of 1,3-dienes and an oxidation process to access 2-(phenylsulfonyl)-1,3-dienes.8 Recently, Sun and Zhang reported a protocol to directly access β-seleno sulfones under mild conditions through selenosulfonylation of alkenes.9 Moreover, Billard and Tlili investigated the reactivity of fluoroalkylselenotoluenesulfonates and developed a visible light-promoted selenosulfonylation of unsaturated compounds through radical intermediates (Scheme 1a).10 Despite these investigations, the enantioselective version of selenosulfonyla© 2019 American Chemical Society

Scheme 1. Selenosulfonylation of C−C Double Bonds

tion reaction was rarely addressed. Recently, we reported the organocatalytic enantioselective addition of selenosulfonates to α,β-unsaturated ketone to realize the asymmetric selenolation of the C−C double bond (Scheme 1b).11a In the development of green methodologies for the enantioselective construction of C−X (X = Se, S) bonds,11 we were interested in the Received: April 9, 2019 Published: May 22, 2019 8100

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry Table 1. Condition Screeninga

development of organocatalytic selenosulfonylation of α,βunsaturated ketones to form two contiguous stereogenic centers. The usage of environment-friendly catalysts and solvents significantly increases the value of a synthetic methodology. The highly stereoselective organocatalytic methodology in an aqueous medium has become one of the hotspots in organic chemistry and has offered unique opportunities to develop sustainable chemical processes.12 Herein, we report our recent results on organocatalyzed asymmetric selenosulfonylation of α,β-unsaturated ketones to construct two contiguous chiral centers in an aqueous environment, and the reaction can be scaled up to decagram without any chromatography technology to give a desired product with high yield and enantioselectivity.

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RESULTS AND DISCUSSION The study started with para-isopropyl-substituted α,β-unsaturated ketone 2a as the substrate and selenosulfonate 1a as the selenosulfonylation agent by using saturated NaCl solution as the solvent. The reaction proceeded at 25 °C in the presence of a small collection of organocatalysts. Catalyst A was first evaluated, and selenosulfonylation adduct 3a was formed with 42% ee in moderate yield. Then, Takemoto catalyst B was tested and resulted in a better enantioselectivity (80% ee, Table 1, entry 2). These results encouraged us to test cinchona alkaloidderived thiourea catalyst C. Consequently, enantiocontrol was improved by catalyst C, but the yield was not significantly increased. Squaramides had been successfully employed as hydrogen bond donor catalysts in a wide range of asymmetric reactions. The distance between the two hydrogen donor atoms of squaramides was longer than that of thioureas.13 Thus, we turned our attention to evaluate a series of squaramide-based organocatalysts. Gratifyingly, catalyst D resulted in the better yield and enantioselectivity (Table 1, entry 4). Hydroxyl cinchona-derived squaramide catalyst E led to the slightly decreased enantioselectivity and yield (Table 1, entry 5). Catalyst F significantly decreased the reaction yield and enantioselectivity. Subsequent evaluation of various aqueous solutions did not lead to further improvements in yield and stereocontrol (Table 1, entries 7−15). With the optimized reaction conditions in hand, we further investigated the substrate scope. Various α-selenyl and βsulfonyl ketones could be synthesized in good enantioselectivities by this straightforward and efficient methodology (Table 2). When the R1 group of selenosulfonates bearing methyl and different halides at para-position of phenyl was well tolerated, expected products 3a−3d were obtained in good yields with good stereoselectivities (up to 90% ee, dr > 20:1). Moreover, the adduct without any substitution group at phenyl groups of selenosulfonate could be formed in good yield and enantioselectivity (Table 2, 3e). Next, we evaluated a series of substrates with substitution groups at different positions of R2 groups on the selenium part. A series of substitution with electrondonating and electron-withdrawing groups on para-position of phenyl were examined under standard conditions, and the adducts were successfully formed with slight variations of enantioselectivities and yields (3f−3h). Notably, the orthosubstituted R2 groups were also tolerated to the reaction system and gave desired products with good chemical yields and enantioselectivities (Table 2, 3i−3k), whereas the bulkier substituent groups such as isopropyl at the ortho-position caused a decreased yield (3l). The substrates with metasubstituted R2 groups were also tolerant to our reaction system and gave the desired products in good yields and enantiose-

entry

catalyst

solvent

yield (%)b

ee (%)c

drd

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

A B C D E F D D D D D D D D D

sat. NaCl sat. NaCl sat. NaCl sat. NaCl sat. NaCl sat. NaCl sat. KCl sat. KBr sat. NH4Cl sat. KI sat. KSCN sat. KBF4 sat. BaCl2 sat. LiCl H2O

55 48 53 85 80 56 80 80 86 76 43 50 45 52 78

42 80 86 90 88 27 87 86 86 84 86 88 62 43 88

>20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1 >20:1

a

Unless otherwise noted, all reactions were carried out with 1a (0.1 mmol), 2a (0.1 mmol), and catalyst (10 mol %) in solvent (1 mL) at 25 °C for 16 h. bIsolated yield. cDetermined by HPLC analysis on a chiral stationary phase. dDiastereomeric ratio (dr) was determined by 1 H NMR.

lectivities (3m−3o). Moreover, the substrates with 2,5disubstituted phenyl groups on the selenium part were also tolerated to this enantioselective selenosulfonylation reaction (3p−3q). After exploring the substrate scope of selenosulfonates, with Se-phenyl 4-methylbenzenesulfonoselenoate (1a) as the counter partner, we investigated the substrate tolerance of α,βunsaturated ketones. As for substitution group R3, a phenyl group bearing normal electron-donating or electron-withdrawing substituents at the para-position allowed good yields and stereocontrol (4a−4j). Notably, excellent enantioselectivity could be achieved through recrystallization from dichloromethane (4j, 96% ee). Nevertheless, when the strong electronwithdrawing group existed at the para-position, the product was obtained with decreased yield (4k). As for the R3 group with the methoxyl group at the ortho-position of phenyl, the corresponding substrate formed product 4l in good yield and enantioselectivity. With interesting fluoro substituent at either the ortho- or meta-position of the phenyl group, adducts 4m and 8101

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry Table 2. Substrate Scopea,b

Reaction conditions: 1 (0.1 mmol), D (10 mol %), and 2a (0.1 mmol) in sat. NaCl solution (1 mL) at 25 °C for 16 h. bDiastereomeric ratio (dr) was determined by 1H NMR and dr > 20:1.

a

4n were formed with good yields and ee values. Moreover, the substrate with R3 bearing 2,4-difluoro-substituted phenyl was also well tolerated to reaction conditions (4p), whereas in the case of the 2,4-dimethyl-substituted substrate, the reaction yield and stereoselectivity were decreased (4o). Interestingly, when R3 groups were naphthyl or heterocyclic rings, the corresponding adducts could be formed in good yields and enantioselectivities (4q−4s). The substrates in which R4 was replaced by other alkyl substituents were also examined, and the products were successfully generated but with lower yields and enantioselectivities (4t and 4u). The absolute configuration of 4u was determined to be (2R,3S) by single-crystal X-ray crystallographic analysis, and others were assigned by analogue. Finally, instead of α,β-unsaturated ketone, allyl alcohol ketone could also be used as the substrate in this enantioselective selenosulfonylation reaction to give desired adduct 4v with the similar result of the alkyl-substituted substrate. It is worth noting that the substrate in which R4 was the aryl group did not react with selenosulfonates to give the desired product; we have investigated chalcones and other β-aryl substituted substrates, and no reaction occurred after 72 h under standard reaction conditions. At the end, we were interested in using cyclic enones as substrates in our reaction system; to our delight, products 4w and 4x were successfully formed under standard reaction conditions, although lower degree of yields and selectivities were observed. Product 4x was determined absolute configuration by

single-crystal X-ray crystallographic analysis, and 4w was assigned by the analogue (Table 3). After the exploration of the reaction substrate scope, we performed some experiments to further demonstrate the practicability of the current reaction. First, a decagram scale reaction of 2k with selenosulfonate 1a under standard reaction conditions was performed (Scheme 2a). The reaction went smoothly to give product 4j with improved yield and enantioselectivity. Notably, the workup procedures of the scaled reaction were modified by a simple slurry of the reaction mixture with acetonitrile. After phase separation and filtration, product 4j was obtained in good yield and ee value (81% yield, 87% ee) was obtained without any chromatography technology. Moreover, the chiral α-selenyl β-sulfone ketone obtained from this reaction was transformed into corresponding alcohol with good stereocontrol. The treatment of 4j (with 96% ee) with NaBH4 and CeCl3·7H2O in MeOH easily generated stereoenriched alcohol bearing selenyl and sulfone functional groups with 74% yield and 93% ee. The configuration of 5 was determined to be (1S,2R,3S) by X-ray analysis. In order to give an insight into the reaction mechanism, a plausible reaction mechanism is depicted in Scheme 3. We speculated that cinchona alkaloid catalyst D might interact with selenosulfonate and α,β-unsaturated ketones 2 to form complex TS-1. The selenium part of TS-1 was then attached to the electron-rich conjugated carbon−carbon double bond, thus forming a stereocontrolled seleniranium ion as transition state 8102

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

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The Journal of Organic Chemistry Table 3. Substrate Scopea,b

Reaction conditions: 1a (0.1 mmol), D (10 mol %), and 2 (0.1 mmol) in sat. NaCl solution (1 mL) at 25 °C for 16 h. bDiastereomeric ratio (dr) was determined by 1H NMR and dr > 20:1. cAfter recrystallization from DCM, up to 96% ee.

a

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TS-2 and releasing one molecule of the sulfone anion. The stereofused TS-2 was then triggered by the previously generated sulfone anion to open the selenium ring from a favored plane to give product 4. Meanwhile, the catalyst was regenerated, thereby closing the catalytic cycle.

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EXPERIMENTAL SECTION

General Information. 1H and 13C{1H} NMR spectra were recorded on an Agilent 400MR DD2 (400 MHz) spectrometer and Agilent 600MR DD2 (600 MHz) spectrometer. Chemical shifts were reported in parts per million (ppm), and tetramethylsilane or the residual solvent peak was used as an internal reference: CDCl3 (1H NMR δ 0.00, 13C{1H} NMR δ 77.00). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad), coupling constants (Hz), and integration. Enantiomeric excesses (ee) were determined by highperformance liquid chromatography (HPLC) analysis on Hitachi Chromaster using DAICEL CHIRALCEL AD-H, 4.6 mm Φ × 250 mm L and DAICEL CHIRALCEL OD-H, 4.6 mm Φ × 250 mm L. The high-resolution mass spectrometry (HRMS) spectra were acquired on 7 T SolariX FT-ICR MS (Bruker Daltonics, Bremen, Germany) with an ESI source. X-ray crystallography analysis of the single crystal was performed on an Agilent SuperNova-CCD X-ray diffractometer. Optical rotation was measured on a Rudolph Autopol I polarimeter. Melting points were measured using a SGWX-4A microscopy melting point meter and are uncorrected. Unless otherwise stated, all reagents were purchased from commercial suppliers and used without further purification.

CONCLUSIONS

In conclusion, we developed an organocatalyzed asymmetric selenosulfonylation reaction of α,β-unsaturated ketones in an aqueous medium. The reaction was characterized by green reaction solvent, mild conditions, and high enantioselectivities. Moreover, the reaction was scalable via a facile workup process to give the desired product in the improved yield and enantioselectivity. Furthermore, the product could be transformed into useful synthons with excellent stereocontrol. The method provides a simple, efficient, and scalable pathway to access stereocontrolled α-selenyl and β-sulfonyl ketones in an aqueous medium with the generation of two contiguous stereogenic centers. 8103

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

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The Journal of Organic Chemistry Scheme 2. Gram-Scale Synthesis and Transformation of 4j

a

Pictures of the reaction processes: (1A) Reaction mixture; (1B) Reaction workup; and (1C) Product 4j. reaction mixture was allowed to cool to room temperature and extracted with CH2Cl2. The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and concentrated in vacuum. The crude product was purified by the chromatograph (PE/EA = 100:1) to afford diphenyl diselenide. Step 2. A suspension of appropriate sodium benzenesulfinates (20.0 mmol, 4.0 equiv) in CH2Cl2 (50 mL) containing diphenyl diselenide (5.0 mmol, 1.0 equiv) was cooled at 0 °C and [bis(trifluoroacetoxy)iodo]benzene (5.5 mmol, 1.1 equiv) in CH2Cl2 (20 mL) was added slowly. Then, the mixture was stirred at room temperature for 3 h. The reaction mixture was washed with H2O and dried over anhydrous Na2SO4. The solvent CH2Cl2 was removed under reduced pressure, and the residue was purified by the chromatograph (PE/EA = 6:1) to afford compounds 1. Selenosulfonates 1a−1q were prepared according to GP-1 and the spectroscopy data are in good agreement with reported values.14 General Procedure for the Synthesis of Substituted (E)-1Phenylbut-2-en-1-ones (GP-2). α,β-Unsaturated ketones 2 are known compounds and were prepared through a three-step procedure according to the literature. Step 1. A solution of appropriate ketone (20.0 mmol, 1.0 equiv) in CHCl3 (15 mL) was added in one portion to a vigorously stirred, refluxing suspension of CuBr2 (40.0 mmol, 2.0 equiv) in ethyl acetate (20 mL). The reaction was practically complete after reflux for 2 h, as indicated by the conversion of CuBr2 (black) into CuBr (white), and then the solid was removed by filtration through Celite. The combined organic layer was washed with 5% Na2CO3 and brine, dried over anhydrous Na2SO4, and evaporated under vacuum to give corresponding 2-bromo-1-phenylethan-1-one used in the next step without further purification. Step 2. A mixture of 2-bromo-1-phenylethan-1-one (10.0 mmol) and triphenylphosphine (10.0 mmol) in toluene (20 mL) was stirred for 24

Scheme 3. Plausible Mechanism

General Procedure for the Synthesis of Selenosulfonates (GP-1). Selenosulfonates 1 are known compounds and were prepared through a two-step procedure according to the literature. Step 1. To a stirred solution of Se0 metal (10.0 mmol, 2.0 equiv) and halides (5.0 mmol, 1.0 equiv) in DMSO (10 mL) were added CuO nanoparticles (0.5 mmol, 0.1 equiv) followed by KOH (10.0 mmol, 2.0 equiv) under the nitrogen atmosphere. The resulting reaction mixture was stirred at 90 °C for 6 h. After the reaction was complete, the 8104

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry h at room temperature. The formed precipitate was filtered and then dissolved in CH2Cl2 (10 mL) followed by Na2CO3 (1.5 equiv) in water (20 mL) was added. After stirred for 2 h, the organic layer was separated, and water was extracted with CH2Cl2. The solvent was removed under vacuum and the solid was washed with PE and then filtrated to give stabilized ylide. Step 3. To a solution of the appropriate stabilized ylide (5.0 mmol) in THF (15 mL) was added aldehyde (15.0 mmol), and the solution was heated under reflux for 3 h. The solution was cooled, and the solvent evaporated in vacuum. The product was purified by chromatography to give 2 and was used immediately. Substituted (E)-1-phenylbut-2-en-1-ones 2a−2v were prepared according to GP-2, and the spectroscopy data are in good agreement with reported values.15 Procedure for the Synthesis of (E)-4-Hydroxy-1-phenylbut2-en-1-one (2w). The reaction was carried out according to a literature method.16 To a solution of the stabilized ylide (3.6 mmol) in THF (15 mL) was added glycoaldehyde dimer (180.0 mg, 1.8 mmol), and the resulting solution was heated under reflux for 3 h. The solution was cooled, and the solvent evaporated under vacuum. The crude product was purified by column chromatography on silica gel (hexane/ EA = 3:1), and the spectroscopy data are in good agreement with reported values. General Procedure for the Synthesis of Compound 3 or 4 (GP-3). The selenosulfonates 1 (0.1 mmol, 1.0 equiv), α,β-unsaturated ketones 2 (0.1 mmol, 1.0 equiv), and catalyst D (0.01 mmol, 0.1 equiv) were added to a 10 mL tube with a magnetic stirring bar, and sat. NaCl solution (1 mL) was injected into the tube. After stirring at 25 °C for 16 h, the reaction mixture was extracted with ethyl acetate and concentrated under vacuum. The crude product was purified by column chromatography on silica gel (DCM/PE = 2:1) to afford 3 or 4. (2R,3S)-1-(4-Isopropylphenyl)-2-(phenylselanyl)-3-tosylbutan-1one (3a). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3a (42.4 mg, 85% yield) as a white solid with an excellent diastereomeric ratio; mp 104−106 °C; 1H NMR (400 MHz, CDCl3): δ 7.74 (d, J = 6.6 Hz, 2H), 7.66 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 6.9 Hz, 2H), 7.36−7.29 (m, 1H), 7.28−7.16 (m, 6H), 4.99 (d, J = 10.1 Hz, 1H), 4.21−4.10 (m, 1H), 3.02−2.89 (m, 1H), 2.37 (s, 3H), 1.73 (d, J = 5.3 Hz, 3H), 1.27 (d, J = 6.8 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 154.4, 144.8, 135.6, 134.9, 133.0, 129.6, 129.3, 129.1, 128.8, 128.7, 127.4, 126.5, 60.3, 46.1, 34.2, 23.7, 21.6, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C26H28NaO3SSe, M + Na]+, 523.0817; found, 523.0816; optical rotation: [α]20 D −49.9° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wave length = 254 nm, tR = 9.494 min (major), tR = 11.147 min (minor). (2R,3S)-3-((4-Fluorophenyl)sulfonyl)-1-(4-isopropylphenyl)-2(phenylselanyl)butan-1-one (3b). According to GP-3, combining selenosulfonate 1b (0.1 mmol, 31.5 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3b (36.2 mg, 72% yield) as a white solid with an excellent diastereomeric ratio; mp 101−102 °C; 1H NMR (400 MHz, CDCl3): δ 7.81−7.71 (m, 4H), 7.39 (d, J = 7.5 Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H), 7.29−7.20 (m, 4H), 7.06 (t, J = 8.4 Hz, 2H), 4.98 (d, J = 10.2 Hz, 1H), 4.20−4.11 (m, 1H), 3.01−2.91 (m, 1H), 1.76 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.4, 165.7 (d, J = 255.0 Hz), 154.6, 135.6, 134.0 (d, J = 3.0 Hz), 132.8, 131.6 (d, J = 10.0 Hz), 129.2, 129.2, 128.6, 127.1, 126.5, 116.2 (d, J = 22.0 Hz), 60.5, 46.0, 34.1, 23.6, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C25H25FNaO3SSe, M + Na]+, 527.0566; found, 527.0565; optical rotation: [α]20 D −173.2° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 10.471 min (major), tR = 14.106 min (minor). (2R,3S)-3-((4-Chlorophenyl)sulfonyl)-1-(4-isopropylphenyl)-2(phenylselanyl)butan-1-one (3c). According to GP-3, combining selenosulfonate 1c (0.1 mmol, 33.2 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3c (42.2 mg, 81% yield) as a white solid with an excellent diastereomeric ratio; mp 121−122 °C; 1H NMR (400 MHz, CDCl3): δ 7.75−7.65 (m, 4H), 7.40 (d, J = 7.2 Hz, 2H),

7.37−7.29 (m, 3H), 7.29−7.21 (m, 4H), 4.95 (d, J = 10.2 Hz, 1H), 4.21−4.10 (m, 1H), 3.02−2.89 (m, 1H), 1.76 (d, J = 7.1 Hz, 3H), 1.28 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 154.6, 140.5, 136.4, 135.6, 132.7, 130.3, 129.3, 129.2, 128.6, 127.10, 126.5, 60.5, 46.0, 34.2, 23.6, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C25H25ClNaO3SSe, M + Na]+, 543.0270; found, 543.0271; optical rotation: [α]D20 −100.3° (c = 1.0, CHCl 3 ); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 11.629 min (major), tR = 15.546 min (minor). (2R,3S)-3-((4-Bromophenyl)sulfonyl)-1-(4-isopropylphenyl)-2(phenylselanyl)butan-1-one (3d). According to GP-3, combining selenosulfonate 1d (0.1 mmol, 37.6 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3d (42.9 mg, 76% yield) as a white solid with an excellent diastereomeric ratio; mp 109−112 °C; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 8.5 Hz, 2H), 7.51 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 7.3 Hz, 2H), 7.35 (t, J = 7.3 Hz, 1H), 7.29−7.22 (m, 4H), 4.95 (d, J = 10.2 Hz, 1H), 4.16 (dq, J = 10.1, 7.1 Hz, 1H), 3.02−2.92 (m, 1H), 1.77 (d, J = 7.1 Hz, 3H), 1.28 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.2, 154.6, 136.9, 135.6, 132.7, 132.2, 130.3, 129.3, 129.2, 129.2, 128.6, 127.1, 126.5, 60.4, 45.9, 34.2, 23.6, 14.7; HRMS (ESI-FT-ICR) m/z: calcd for [C25H25BrNaO3SSe, M + Na]+, 586.9765; found, 586.9764; optical rotation: [α]20 D −58.3° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 12.307 min (major), tR = 16.350 min (minor). (2R,3S)-1-(4-Isopropylphenyl)-2-(phenylselanyl)-3(phenylsulfonyl)butan-1-one (3e). According to GP-3, combining selenosulfonate 1e (0.1 mmol, 29.8 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3e (34.0 mg, 70% yield) as a white solid with an excellent diastereomeric ratio; mp 108−111 °C; 1H NMR (400 MHz, CDCl3): δ 7.82−7.72 (m, 4H), 7.57 (t, J = 7.4 Hz, 1H), 7.48−7.38 (m, 4H), 7.33 (t, J = 7.3 Hz, 1H), 7.25 (d, J = 8.0 Hz, 4H), 5.01 (d, J = 10.1 Hz, 1H), 4.17 (dq, J = 9.8, 7.1 Hz, 1H), 3.02−2.91 (m, 1H), 1.73 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 154.4, 138.0, 135.6, 133.7, 133.0, 129.2, 129.1, 129.0, 128.7, 128.7, 127.3, 126.5, 60.3, 46.0, 34.1, 23.6, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C25H26NaO3SSe, M + Na]+, 509.0660; found, 509.0662; optical rotation: [α]20 D −96.4° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 14.986 min (major), tR = 18.532 min (minor). (2R,3S)-1-(4-Isopropylphenyl)-2-(p-tolylselanyl)-3-tosylbutan-1one (3f). According to GP-3, combining selenosulfonate 1f (0.1 mmol, 32.5 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3f (28.2 mg, 55% yield) as a white solid with an excellent diastereomeric ratio; mp 80−82 °C; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 8.0 Hz, 2H), 7.64 (d, J = 7.9 Hz, 2H), 7.25 (t, J = 8.1 Hz, 4H), 7.18 (d, J = 7.9 Hz, 2H), 7.03 (d, J = 7.7 Hz, 2H), 4.93 (d, J = 10.2 Hz, 1H), 4.12 (dq, J = 14.4, 7.1 Hz, 1H), 3.00−2.92 (m, 1H), 2.35 (s, 3H), 2.32 (s, 3H), 1.73 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13 C{1H} NMR (100 MHz, CDCl3): δ 192.4, 154.3, 144.7, 139.4, 135.9, 135, 133.0, 130.0, 129.6, 128.8, 128.7, 126.4, 123.5, 60.3, 46.1, 34.2, 23.7, 21.5, 21.2, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C27H30NaO3SSe, M + Na]+, 537.0973; found, 537.0972; optical rotation: [α]D20 −101.5° (c = 1.0, CHCl 3 ); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 11.373 min (major), tR = 13.154 min (minor). (2R,3S)-2-((4-Fluorophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3g). According to GP-3, combining selenosulfonate 1g (0.1 mmol, 32.9 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3g (29.9 mg, 58% yield) as a white solid with an excellent diastereomeric ratio; mp 118−119 °C; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.1 Hz, 2H), 7.65 (d, J = 8.1 Hz, 2H), 7.38−7.31 (m, 2H), 7.24 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.90 (t, J = 8.5 Hz, 2H), 4.98 (d, J = 9.9 Hz, 1H), 4.08 (dq, J = 14.3, 7.1 Hz, 1H), 3.00−2.89 (m, 1H), 2.35 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 163.4 (d, J = 249.0 Hz), 154.5, 144.8, 138.3 (d, J = 8.0 Hz), 134.8, 133.0, 129.6, 8105

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry

min, wavelength = 254 nm, tR = 9.915 min (major), tR = 10.812 min (minor). (2R,3S)-1-(4-Isopropylphenyl)-2-((2-isopropylphenyl)selanyl)-3tosylbutan-1-one (3l). According to GP-3, combining selenosulfonate 1l (0.1 mmol, 35.3 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3l (22.8 mg, 42% yield) as a white solid with an excellent diastereomeric ratio; mp 62−64 °C; 1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 7.7 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.21 (d, J = 8.0 Hz, 2H), 7.18− 7.11 (m, 3H), 7.07 (t, J = 7.4 Hz, 1H), 5.06 (d, J = 9.9 Hz, 1H), 4.32− 4.23 (m, 1H), 3.15−3.06 (m, 1H), 2.94−2.85 (m, 1H), 2.36 (s, 3H), 1.73 (d, J = 7.1 Hz, 3H), 1.22 (d, J = 6.9 Hz, 6H), 1.01 (d, J = 6.8 Hz, 3H), 0.90 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.4, 154.3, 151.6, 144.8, 135.4, 134.7, 132.9, 129.6, 129.2, 129.1, 128.8, 128.6, 126.8, 126.2, 125.7, 60.4, 46.4, 34.1, 32.7, 24.1, 23.6, 23.1, 21.5, 14.9; HRMS (ESI-FT-ICR) m/z: calcd for [C29H34NaO3SSe, M + Na]+, 565.1286; found, 565.1288; optical rotation: [α]20 D −155.2° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 8.355 min (major), tR = 10.548 min (minor). (2R,3S)-1-(4-Isopropylphenyl)-2-(m-tolylselanyl)-3-tosylbutan-1one (3m). According to GP-3, combining selenosulfonate 1m (0.1 mmol, 32.5 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3m (30.0 mg, 58% yield) as a white solid with an excellent diastereomeric ratio; mp 84−86 °C; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.1 Hz, 2H), 7.66 (d, J = 8.0 Hz, 2H), 7.28−7.17 (m, 6H), 7.12 (d, J = 4.7 Hz, 2H), 4.97 (d, J = 10.1 Hz, 1H), 4.22−4.13 (m, 1H), 3.00−2.91 (m, 1H), 2.38 (s, 3H), 2.26 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.9, 154.4, 144.8, 139.1, 136.2, 135.0, 133.1, 132.5, 129.9, 129.6, 129.1, 128.9, 128.8, 127.4, 126.4, 60.4, 46.2, 34.2, 23.7, 21.6, 21.2, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C27H30NaO3SSe, M + Na]+, 537.0973; found, 537.0972; optical rotation: [α]20 D −67.3° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 10.486 min (major), tR = 11.392 min (minor). (2R,3S)-2-((3-Chlorophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3n). According to GP-3, combining selenosulfonate 1n (0.1 mmol, 34.6 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3n (31.5 mg, 59% yield) as a white solid with an excellent diastereomeric ratio; mp 64−66 °C; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.2 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.36−7.17 (m, 7H), 7.14 (t, J = 7.8 Hz, 1H), 5.05 (d, J = 9.8 Hz, 1H), 4.15 (dq, J = 14.3, 7.1 Hz, 1H), 2.99−2.89 (m, 1H), 2.33 (s, 3H), 1.69 (d, J = 7.1 Hz, 3H), 1.25 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.4, 154.4, 144.7, 135.1, 134.5, 134.2, 133.5, 132.8, 130.12, 129.5, 129.1, 128.6, 128.5, 128.5, 126.0, 59.9, 46.0, 34.0, 23.4, 21.4, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C26H27ClNaO3SSe, M + Na]+, 557.0427; found, 557.0425; optical rotation: [α]20 D −105.8° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.319 min (major), tR = 13.137 min (minor). (2R,3S)-2-((3-Bromophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3o). According to GP-3, combining selenosulfonate 1o (0.1 mmol, 39.0 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3o (35.4 mg, 61% yield) as a white solid with an excellent diastereomeric ratio; mp 64−67 °C; 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.47 (s, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 7.6 Hz, 1H), 7.28−7.19 (m, 4H), 7.10 (t, J = 7.8 Hz, 1H), 5.04 (d, J = 9.8 Hz, 1H), 4.19−4.08 (m, 1H), 3.01−2.89 (m, 1H), 2.36 (s, 3H), 1.69 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 154.6, 144.8, 138.1, 134.6, 134.1, 132.8, 132.1, 130.5, 129.6, 128.9, 128.8, 128.6, 126.5, 122.5, 60.1, 46.1, 34.1, 23.6, 21.5, 14.9; HRMS (ESI-FTICR) m/z: calcd for [C26H27BrNaO3SSe, M + Na]+, 600.9922; found, 600.9924; CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.188 min (major), tR = 14.017 min (minor). (2R,3S)-2-((5-Fluoro-2-methylphenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3p). According to GP-3, combining

128.8, 128.6, 126.4, 121.5 (d, J = 4.0 Hz), 116.41 (d, J = 22.0 Hz), 60.0, 45.9, 34.1, 23.6, 21.5, 14.9; HRMS (ESI-FT-ICR) m/z: calcd for [C26H27FNaO3SSe, M + Na]+, 541.0722; found, 541.0723; HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.312 min (major), tR = 13.970 min (minor). (2R,3S)-2-((4-Chlorophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3h). According to GP-3, combining selenosulfonate 1h (0.1 mmol, 34.6 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3h (30.0 mg, 56% yield) as a white solid with an excellent diastereomeric ratio; mp 113−115 °C; 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 7.9 Hz, 2H), 7.65 (d, J = 7.9 Hz, 2H), 7.32−7.21 (m, 4H), 7.18 (t, J = 8.9 Hz, 4H), 5.01 (d, J = 9.8 Hz, 1H), 4.14−4.05 (m, 1H), 2.99−2.90 (m, 1H), 2.34 (s, 3H), 1.70 (d, J = 7.0 Hz, 3H), 1.26 (d, J = 6.8 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 154.5, 144.7, 137.1, 135.6, 134.6, 132.8, 129.5, 129.3, 128.7, 128.6, 126.4, 125.0, 59.9, 45.8, 34.0, 23.5, 21.4, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C26H27ClO3SSe, M + Na]+, 557.0427; found, 557.0425; optical rotation: [α]20 D −78.1° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 11.062 min (major), tR = 12.770 min (minor). (2R,3S)-2-((2-Chlorophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3i). According to GP-3, combining selenosulfonate 1i (0.1 mmol, 34.6 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3i (38.6 mg, 72% yield) as a white solid with an excellent diastereomeric ratio; mp 108−110 °C; 1H NMR (400 MHz, CDCl3): δ 7.72−7.66 (m, 4H), 7.46 (d, J = 7.7 Hz, 1H), 7.34 (d, J = 7.9 Hz, 1H), 7.26−7.16 (m, 5H), 7.11 (t, J = 7.5 Hz, 1H), 5.27 (d, J = 10.1 Hz, 1H), 4.37−4.26 (m, 1H), 2.98−2.87 (m, 1H), 2.38 (s, 3H), 1.67 (d, J = 7.1 Hz, 3H), 1.25 (d, J = 6.8 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.4, 154.5, 144.8, 137.0, 134.7, 134.5, 132.9, 129.7, 129.6, 129.5, 128.8, 128.6, 127.4, 126.3, 60.5, 44.8, 34.1, 23.6, 21.5, 14.4; HRMS (ESI-FT-ICR) m/z: calcd for [C26H27ClNaO3SSe, M + Na]+, 557.0427; found, 557.0425; optical rotation: [α]20 D −194.2° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 18.369 min (minor), tR = 23.586 min (major). (2R,3S)-2-((2-Bromophenyl)selanyl)-1-(4-isopropylphenyl)-3-tosylbutan-1-one (3j). According to GP-3, combining selenosulfonate 1j (0.1 mmol, 39.0 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3j (39.3 mg, 68% yield) as a white solid with an excellent diastereomeric ratio; mp 109−110 °C; 1H NMR (400 MHz, CDCl3): δ 7.70 (t, J = 6.9 Hz, 4H), 7.53−7.44 (m, 2H), 7.28−7.14 (m, 5H), 7.10 (t, J = 7.5 Hz, 1H), 5.29 (d, J = 10.1 Hz, 1H), 4.40−4.29 (m, 1H), 2.98−2.87 (m, 1H), 2.38 (s, 3H), 1.66 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.8 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.5, 154.6, 144.9, 134.6, 133.9, 133.0, 132.9, 131.5, 129.6, 129.3, 128.8, 128.6, 128.1, 127.2, 126.4, 60.5, 45.2, 34.1, 23.6, 21.5, 14.4; HRMS (ESI-FTICR) m/z: calcd for [C26H27BrNaO3SSe, M + Na]+, 600.9922; found, 600.9924; optical rotation: [α]20 D −143.8° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 21.059 min (minor), tR = 27.951 min (major). (2R,3S)-1-(4-Isopropylphenyl)-2-(o-tolylselanyl)-3-tosylbutan-1one (3k). According to GP-3, combining selenosulfonate 1k (0.1 mmol, 32.5 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3k (28.0 mg, 55% yield) as a white solid with an excellent diastereomeric ratio; mp 82−84 °C; 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 8.1 Hz, 2H), 7.61 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 7.7 Hz, 1H), 7.25−7.12 (m, 5H), 7.09 (d, J = 7.3 Hz, 1H), 7.04 (t, J = 7.4 Hz, 1H), 5.08 (d, J = 9.9 Hz, 1H), 4.31−4.22 (m, 1H), 2.96−2.86 (m, 1H), 2.37 (s, 3H), 2.15 (s, 3H), 1.71 (d, J = 7.1 Hz, 3H), 1.24 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.6, 154.4, 144.7, 141.4, 135.2, 134.7, 133.0, 130.2, 129.6, 129.4, 128.9, 128.8, 128.6, 126.8, 126.2, 60.4, 45.4, 34.1, 23.6, 22.5, 21.5, 14.8; HRMS (ESI-FT-ICR) m/ z: calcd for [C27H30NaO3SSe, M + Na]+, 537.0973; found, 537.0972; optical rotation: [α]20 D −169.1° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ 8106

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry selenosulfonate 1p (0.1 mmol, 34.3 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3p (36.2 mg, 68% yield) as a white solid with an excellent diastereomeric ratio; mp 53−55 °C; 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.1 Hz, 2H), 7.63 (d, J = 8.2 Hz, 2H), 7.27−7.22 (m, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.12−7.03 (m, 2H), 6.86 (t, J = 8.3 Hz, 1H), 5.09 (d, J = 9.8 Hz, 1H), 4.31−4.21 (m, 1H), 2.97−2.87 (m, 1H), 2.38 (s, 3H), 2.15 (s, 3H), 1.68 (d, J = 7.2 Hz, 3H), 1.24 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.5, 160.4 (d, J = 247.0 Hz), 154.6, 144.9, 136.9 (d, J = 3.0 Hz), 134.5, 133.0, 131.5 (d, J = 8.0 Hz), 130.1 (d, J = 6.0 Hz), 129.7, 128.8, 128.6, 126.3, 121.6 (d, J = 22.0 Hz), 115.7 (d, J = 21.0 Hz), 60.2, 45.4, 34.1, 23.6, 21.6, 21.5, 14.7; HRMS (ESI-FT-ICR) m/z: calcd for [C27H29FNaO3SSe, M + Na]+, 555.0879; found, 555.0881; optical rotation: [α] D20 −129.0° (c = 1.0, CHCl3 ); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 17.497 min (major), tR = 18.425 min (minor). (2R,3S)-2-((2,5-Difluorophenyl)selanyl)-1-(4-isopropylphenyl)-3tosylbutan-1-one (3q). According to GP-3, combining selenosulfonate 1q (0.1 mmol, 34.7 mg) and α,β-unsaturated ketone 2a (0.1 mmol, 18.8 mg) gave compound 3q (39.6 mg, 74% yield) as a white solid with an excellent diastereomeric ratio; mp 89−92 °C; 1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 7.9 Hz, 2H), 7.67 (d, J = 7.8 Hz, 2H), 7.29−7.19 (m, 4H), 7.00 (t, J = 5.8 Hz, 3H), 5.14 (d, J = 10.2 Hz, 1H), 4.19 (dq, J = 14.7, 7.1 Hz, 1H), 3.01−2.91 (m, 1H), 2.38 (s, 3H), 1.70 (d, J = 7.1 Hz, 3H), 1.27 (d, J = 6.9 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 158.9 (dd, J = 240.0, 2.0 Hz), 157.9 (dd, J = 246.0, 2.0 Hz), 157.7, 156.7, 156.7, 154.8 144.9, 134.7, 132.8, 129.7, 128.9, 128.7, 126.5, 123.6 (dd, J = 24.5, 1.0 Hz), 118.1 (dd, J = 24.0, 8.0 Hz), 116.4 (dd, J = 27.0, 9.0 Hz), 115.1 (dd, J = 26.0, 7.0 Hz), 60.5, 45.6, 34.2, 23.6, 21.6, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C26H26F2NaO3SSe, M + Na]+, 559.0628; found, 559.0627; optical rotation: [α]20 D −67.7° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 13.753 min (minor), tR = 17.220 min (major). (2R,3S)-1-Phenyl-2-(phenylselanyl)-3-tosylbutan-1-one (4a). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2b (0.1 mmol, 14.6 mg) gave compound 4a (33.4 mg, 73% yield) as a white solid with an excellent diastereomeric ratio; mp 90−91 °C; 1H NMR (400 MHz, CDCl3): δ 7.81 (d, J = 7.7 Hz, 2H), 7.66 (d, J = 7.9 Hz, 2H), 7.53 (t, J = 7.2 Hz, 1H), 7.44−7.36 (m, 4H), 7.36−7.30 (m, 1H), 7.26−7.19 (m, 4H), 4.99 (d, J = 10.1 Hz, 1H), 4.20−4.10 (m, 1H), 2.37 (s, 3H), 1.73 (d, J = 7.1 Hz, 3H); 13 C{1H} NMR (100 MHz, CDCl3): δ 192.8, 144.8, 135.6, 135.3, 134.8, 132.8, 129.6, 129.3, 129.2, 128.8, 128.4, 128.3, 127.2, 60.2, 46.3, 21.5, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C23H22NaO3SSe, M + Na]+, 481.0347; found, 481.0346; optical rotation: [α]20 D −126.5° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 85:15, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.870 min (major), tR = 14.112 min (minor). (2R,3S)-2-(Phenylselanyl)-1-(p-tolyl)-3-tosylbutan-1-one (4b). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2c (0.1 mmol, 16.0 mg) gave compound 4b(39.3 mg, 83% yield) as a white solid with an excellent diastereomeric ratio; mp 120−121 °C; 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 8.1 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.40 (d, J = 7.4 Hz, 2H), 7.34 (t, J = 7.4 Hz, 1H), 7.25 (d, J = 7.2 Hz, 2H), 7.23−7.16 (m, 4H), 4.98 (d, J = 10.1 Hz, 1H), 4.20−4.08 (m, 1H), 2.42 (s, 3H), 2.38 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.5, 144.8, 143.8, 135.6, 134.9, 132.6, 129.6, 129.2, 129.1, 129.1, 128.8, 128.6, 127.4, 60.3, 46.2, 21.6, 21.5, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C24H24NaO3SSe, M + Na]+, 495.0504; found, 495.0501; optical rotation: [α] D20 −122.9° (c = 1.0, CHCl3 ); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 85:15, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 15.658 min (major), tR = 21.293 min (minor). (2R,3S)-1-(4-(tert-Butyl)phenyl)-2-(phenylselanyl)-3-tosylbutan1-one (4c). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2d (0.1 mmol, 20.2 mg) gave compound 4c (37.9 mg, 74% yield) as a white solid with an

excellent diastereomeric ratio; mp 119−120 °C; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 8.4 Hz, 2H), 7.65 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.1 Hz, 4H), 7.30 (t, J = 7.3 Hz, 1H), 7.24−7.14 (m, 4H), 5.01 (d, J = 10.1 Hz, 1H), 4.20−4.11 (m, 1H), 2.32 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H), 1.33 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.4, 156.4, 144.6, 135.4, 134.7, 132.4, 129.5, 129.1, 129.0, 128.7, 128.3, 127.3, 125.2, 60.2, 45.9, 34.9, 30.9, 21.4, 14.9; HRMS (ESI-FT-ICR) m/z: calcd for [C27H30NaO3SSe, M + Na]+, 537.0973; found, 537.0972; optical rotation: [α]20 D −124.5° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 16.763 min (minor), tR = 17.608 min (major). (2R,3S)-1-(4-Isobutylphenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4d). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2e (0.1 mmol, 20.2 mg) gave compound 4d (34.9 mg, 68% yield) as a white solid with an excellent diastereomeric ratio; mp 94−95 °C; 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 7.3 Hz, 2H), 7.33 (t, J = 7.3 Hz, 1H), 7.26 (d, J = 4.0 Hz, 1H), 7.24−7.18 (m, 3H), 7.16 (d, J = 8.0 Hz, 2H), 4.99 (d, J = 10.0 Hz, 1H), 4.15 (dq, J = 14.4, 7.1 Hz, 1H), 2.53 (d, J = 7.1 Hz, 2H), 2.37 (s, 3H), 1.96−1.85 (m, 1H), 1.73 (d, J = 7.1 Hz, 3H), 0.93 (d, J = 6.5 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.7, 147.4, 144.8, 135.6, 134.9, 132.9, 129.6, 129.3, 129.1, 129.1, 128.8, 128.5, 127.4, 60.2, 46.2, 45.3, 30.1, 22.3, 21.5, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C27H30NaO3SSe, M + Na]+, 537.0973; found, 537.0972; optical rotation: [α]20 D −97.0° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 8.496 min (major), tR = 11.212 min (minor). (2R,3S)-2-(Phenylselanyl)-3-tosyl-1-(4-(trifluoromethyl)phenyl)butan-1-one (4e). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2f (0.1 mmol, 21.4 mg) gave compound 4e (41.8 mg, 80% yield) as a white solid with an excellent diastereomeric ratio; mp 120−123 °C; 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.1 Hz, 2H), 7.67 (t, J = 7.7 Hz, 4H), 7.35 (t, J = 6.8 Hz, 3H), 7.29−7.22 (m, 4H), 4.95 (d, J = 10.4 Hz, 1H), 4.13 (dq, J = 10.2, 7.1 Hz, 1H), 2.40 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.9, 145.0, 138.5, 135.7, 134.8, 134.0 (q, J = 33.0 Hz), 129.8, 129.5, 129.4, 128.8, 128.7, 126.9, 125.4 (q, J = 3.0 Hz), 123.6 (q, J = 271.0 Hz), 60.2, 46.5, 21.6, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C24H21F3NaO3SSe, M + Na]+, 549.0221; found, 549.0220; optical rotation: [α]20 D −124.0° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 7.713 min (minor), tR = 14.412 min (major). (2R,3S)-1-([1,1′-Biphenyl]-4-yl)-2-(phenylselanyl)-3-tosylbutan1-one (4f). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2g (0.1 mmol, 22.2 mg) gave compound 4f (33.6 mg, 63% yield) as a white solid with an excellent diastereomeric ratio; mp 142−143 °C; 1H NMR (400 MHz, CDCl3): δ 7.88 (d, J = 8.2 Hz, 2H), 7.68 (d, J = 7.9 Hz, 2H), 7.65−7.58 (m, 4H), 7.48 (t, J = 7.5 Hz, 2H), 7.44−7.38 (m, 3H), 7.34 (t, J = 7.4 Hz, 1H), 7.28−7.20 (m, 4H), 5.03 (d, J = 10.0 Hz, 1H), 4.18 (dq, J = 10.3, 7.1 Hz, 1H), 2.38 (s, 3H), 1.75 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.5, 146.0, 144.8, 139.9, 135.7, 134.9, 134.0, 129.7, 129.3, 129.2, 129.1, 128.9, 128.8, 128.2, 127.4, 127.2, 127.0, 60.3, 46.4, 21.6, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C29H26NaO3SSe, M + Na]+, 557.0660; found, 557.0661; optical rotation: [α]20 D −41.8° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 85:15, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 28.330 min (minor), tR = 31.040 min (major). (2R,3S)-1-(4-Methoxyphenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4g). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2h (0.1 mmol, 17.6 mg) gave compound 4g (32.0 mg, 66% yield) as a white solid with an excellent diastereomeric ratio; mp 108−109 °C; 1H NMR (400 MHz, CDCl3): δ 7.78 (d, J = 8.2 Hz, 2H), 7.65 (d, J = 7.6 Hz, 2H), 7.41 (d, J = 7.2 Hz, 2H), 7.36−7.30 (m, 1H), 7.28−7.16 (m, 4H), 6.87 (d, J = 8.2 Hz, 2H), 4.97 (d, J = 9.8 Hz, 1H), 4.21−4.09 (m, 1H), 3.86 (s, 3H), 2.37 (s, 3H), 1.72 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.8, 8107

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry

(2R,3S)-1-(2-Methoxyphenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4l). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2m (0.1 mmol, 17.6 mg) gave compound 4l (37.7 mg, 77% yield) as a white solid with an excellent diastereomeric ratio; mp 93−95 °C; 1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 7.5 Hz, 1H), 7.70 (d, J = 7.9 Hz, 2H), 7.40 (t, J = 7.5 Hz, 1H), 7.34 (d, J = 7.3 Hz, 2H), 7.28−7.13 (m, 5H), 6.97 (t, J = 7.4 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 5.51 (d, J = 8.9 Hz, 1H), 4.19−4.08 (m, 1H), 3.63 (s, 3H), 2.33 (s, 3H), 1.68 (d, J = 7.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.6, 158.0, 144.5, 134.8, 134.8, 133.6, 132.0, 129.4, 128.8, 128.7, 128.4, 127.8, 125.1, 120.4, 111.4, 59.6, 55.2, 50.4, 21.4, 14.6; HRMS (ESI-FT-ICR) m/z: calcd for [C24H24NaO4SSe, M + Na]+, 511.0453; found, 511.0452; optical rotation: [α]20 D −96.6° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.794 min (major), tR = 16.552 min (minor). (2R,3S)-1-(2-Fluorophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4m). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2n (0.1 mmol, 16.4 mg) gave compound 4m (35.7 mg, 75% yield) as a white solid with an excellent diastereomeric ratio; mp 82−84 °C; 1H NMR (400 MHz, CDCl3): δ 7.84 (t, J = 7.0 Hz, 1H), 7.70 (d, J = 8.1 Hz, 2H), 7.50 (q, J = 6.7, 6.3 Hz, 1H), 7.39−7.29 (m, 3H), 7.28−7.17 (m, 5H), 7.13−7.05 (m, 1H), 5.00 (d, J = 10.2 Hz, 1H), 4.12 (dq, J = 15.2, 7.1 Hz, 1H), 2.37 (s, 3H), 1.68 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 189.2, 161.2 (d, J = 253.0 Hz), 144.8, 135.7, 134.9, 134.5 (d, J = 9.0 Hz), 131.7 (d, J = 2.0 Hz), 129.7, 129.2, 128.9, 126.4, 124.4 (d, J = 3.0 Hz), 123.94 (d, J = 11.0 Hz), 116.6 (d, J = 25.0 Hz), 60.0, 50.2, 21.6, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C23H21FNaO3SSe, M + Na]+, 499.0253; found, 499.0250; optical rotation: [α]20 D −56.3° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 7.558 min (major), tR = 8.444 min (minor). (2R,3S)-1-(3-Fluorophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4n). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2o (0.1 mmol, 16.4 mg) gave compound 4n (37.7 mg, 79% yield) as a white solid with an excellent diastereomeric ratio; mp 110−111 °C; 1H NMR (400 MHz, CDCl3): δ 7.67 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 7.7 Hz, 1H), 7.49 (d, J = 9.5 Hz, 1H), 7.42−7.32 (m, 4H), 7.26 (t, J = 7.8 Hz, 5H), 4.90 (d, J = 10.3 Hz, 1H), 4.12 (dq, J = 10.2, 7.1 Hz, 1H), 2.40 (s, 3H), 1.73 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.6, 162.7 (d, J = 246.0 Hz), 145.0, 137.6 (d, J = 6.0 Hz), 135.8, 134.8, 130.0 (d, J = 8.0 Hz), 129.8, 129.4, 129.4, 128.8, 127.0, 124.1 (d, J = 3.0 Hz), 119.9 (d, J = 21.0 Hz), 115.4 (d, J = 23.0 Hz), 60.2, 46.4, 21.6, 15.1; HRMS (ESI-FTICR) m/z: calcd for [C23H21FNaO3SSe, M + Na]+, 499.0253; found, 499.0250; optical rotation: [α]20 D −111.1° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 16.600 min (major), tR = 17.495 min (minor). (2R,3S)-1-(2,4-Dimethylphenyl)-2-(phenylselanyl)-3-tosylbutan1-one (4o). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2p (0.1 mmol, 17.4 mg) gave compound 4o (26.2 mg, 54% yield) as a white solid with an excellent diastereomeric ratio; mp 84−86 °C; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 8.1 Hz, 2H), 7.55 (d, J = 7.9 Hz, 1H), 7.34−7.23 (m, 5H), 7.16 (t, J = 7.5 Hz, 2H), 7.06 (s, 1H), 6.95 (d, J = 7.8 Hz, 1H), 4.89 (d, J = 9.7 Hz, 1H), 4.16 (dq, J = 9.5, 7.1 Hz, 1H), 2.46 (s, 3H), 2.42 (s, 3H), 2.35 (s, 3H), 1.63 (d, J = 7.2 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 195.5, 144.8, 141.9, 139.8, 135.2, 134.9, 133.4, 132.4, 129.8, 129.2, 128.7, 128.7, 128.3, 126.0, 60.0, 50.2, 21.6, 21.4, 21.0, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C25H26NaO3SSe, M + Na]+, 509.0660; found, 509.0661; optical rotation: [α]20 D −137.4° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 12.135 min (minor), tR = 21.687 min (major). (2R,3S)-1-(2,4-Difluorophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4p). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2q (0.1 mmol, 18.2 mg) gave compound 4p (36.0 mg, 73% yield) as a white solid with an excellent

163.4, 144.8, 135.6, 134.9, 130.8, 129.6, 129.3, 129.1, 128.8, 128.1, 127.6, 113.6, 60.4, 55.4, 46.0, 21.5, 15.0; HRMS (ESI-FT-ICR) m/z: calcd for [C24H24NaO4SSe, M + Na]+, 511.0453; found, 511.0452; optical rotation: [α]20 D −113.6° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 20.260 min (minor), tR = 27.463 min (major). (2R,3S)-1-(4-Fluorophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4h). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2i (0.1 mmol, 16.4 mg) gave compound 4h (31.4 mg, 66% yield) as a white solid with an excellent diastereomeric ratio; mp 104−105 °C; 1H NMR (400 MHz, CDCl3): δ 7.87−7.79 (m, 2H), 7.67 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 7.1 Hz, 2H), 7.34 (d, J = 7.3 Hz, 1H), 7.29−7.21 (m, 4H), 7.07 (t, J = 8.6 Hz, 2H), 4.94 (d, J = 10.2 Hz, 1H), 4.14 (dq, J = 10.2, 7.1 Hz, 1H), 2.39 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.6, 165.6 (d, J = 253.0 Hz), 144.9, 135.6, 134.8, 131.8 (d, J = 3.0 Hz), 131.1 (d, J = 9.0 Hz), 129.7, 129.4, 129.3, 128.8, 127.2, 115.5 (d, J = 22.0 Hz), 60.3, 46.2, 21.5, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C23H21FNaO3SSe, M + Na]+, 499.0253; found, 499.0250; optical rotation: [α] D20 −126.9° (c = 1.0, CHCl3 ); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 8.246 min (minor), tR = 9.714 min (major). (2R,3S)-1-(4-Chlorophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4i). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2j (0.1 mmol, 18.0 mg) gave compound 4i (34.0 mg, 69% yield) as a white solid with an excellent diastereomeric ratio; mp 125−126 °C; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 8.5 Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H), 7.51−7.30 (m, 5H), 7.30−7.19 (m, 4H), 4.92 (d, J = 10.3 Hz, 1H), 4.13 (dq, J = 10.2, 7.1 Hz, 1H), 2.39 (s, 3H), 1.71 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.4, 144.7, 138.9, 135.5, 134.6, 133.6, 129.7, 129.5, 129.2, 129.2, 128.5, 128.4, 126.8, 60.1, 46.0, 21.3, 14.9; HRMS (ESI-FT-ICR) m/z: calcd for [C23H21ClNaO3SSe, M + Na]+, 514.9957; found, 514.9954; optical rotation: [α]20 D −118.0° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 75:25, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 24.652 min (minor), tR = 32.588 min (major). (2R,3S)-1-(4-Bromophenyl)-2-(phenylselanyl)-3-tosylbutan-1one (4j). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2k (0.1 mmol, 22.5 mg) gave compound 4j (33.0 mg, 62% yield) as a white solid with an excellent diastereomeric ratio; mp 146−148 °C; 1H NMR (400 MHz, CDCl3): δ 7.71−7.62 (m, 4H), 7.54 (d, J = 8.3 Hz, 2H), 7.40−7.32 (m, 3H), 7.26 (t, J = 6.4 Hz, 4H), 4.91 (d, J = 10.2 Hz, 1H), 4.12 (dq, J = 14.4, 7.1 Hz, 1H), 2.40 (s, 3H), 1.71 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.0, 145.0, 135.7, 134.8, 134.2, 131.6, 130.0, 129.7, 129.4, 129.4, 128.8, 128.0, 127.1, 60.2, 46.2, 21.6, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C23H21BrNaO3SSe, M + Na]+, 558.9452; found, 558.9451; optical rotation: [α]20 D −101.7° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 9.244 min (minor), tR = 13.824 min (major). (2R,3S)-1-(4-Nitrophenyl)-2-(phenylselanyl)-3-tosylbutan-1-one (4k). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2l (0.1 mmol, 19.1 mg) gave compound 4k (20.6 mg, 41% yield) as a white solid with an excellent diastereomeric ratio; mp 130−131 °C; 1H NMR (400 MHz, CDCl3): δ 8.25 (d, J = 8.7 Hz, 2H), 7.99 (d, J = 8.7 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 7.5 Hz, 3H), 7.32−7.23 (m, 4H), 4.94 (d, J = 10.5 Hz, 1H), 4.12 (dq, J = 10.4, 7.1 Hz, 1H), 2.42 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 191.3, 150.0, 145.2, 140.7, 135.7, 134.7, 129.9, 129.7, 129.6, 129.5, 128.7, 126.7, 123.6, 60.3, 46.8, 21.6, 15.2; HRMS (ESI-FT-ICR) m/z: calcd for [C23H21NNaO5SSe, M + Na]+, 526.0198; found, 526.0195; optical rotation: [α]20 D −20.7° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 60:40, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 16.600 min (minor), tR = 32.458 min (major). 8108

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

The Journal of Organic Chemistry diastereomeric ratio; mp 119−120 °C; 1H NMR (400 MHz, CDCl3): δ 7.94−7.85 (m, 1H), 7.69 (d, J = 8.0 Hz, 2H), 7.40−7.29 (m, 3H), 7.28−7.17 (m, 4H), 6.94 (t, J = 7.3 Hz, 1H), 6.83 (t, J = 10.0 Hz, 1H), 4.94 (d, J = 10.4 Hz, 1H), 4.16−4.06 (m, 1H), 2.37 (s, 3H), 1.66 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 187.9, 165.6 (dd, J = 255.0, 12.0 Hz), 161.7 (dd, J = 256.0, 13.0 Hz), 144.8, 135.6, 134.7, 133.5 (dd, J = 10.0, 3.0 Hz), 129.6, 129.2, 129.2, 128.7, 126.1, 120.5 (dd, J = 11.0, 3.0 Hz), 112.0 (dd, J = 21.0, 3.0 Hz), 104.6 (dd, J = 28.0, 26.0 Hz), 59.90, 49.8, 21.5, 14.9; HRMS (ESI-FT-ICR) m/z: calcd for [C23H20F2NaO3SSe, M + Na]+, 517.0159; found, 517.0158; optical rotation: [α]20 D −24.9° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 10.115 min (minor), tR = 12.163 min (major). (2R,3S)-1-(Naphthalen-2-yl)-2-(phenylselanyl)-3-tosylbutan-1one (4q). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2r (0.1 mmol, 19.6 mg) gave compound 4q (37.2 mg, 73% yield) as a white solid with an excellent diastereomeric ratio; mp 138−140 °C; 1H NMR (400 MHz, CDCl3): δ 8.20 (s, 1H), 7.91 (d, J = 8.6 Hz, 1H), 7.87−7.82 (m, 2H), 7.78 (d, J = 8.0 Hz, 1H), 7.67 (d, J = 8.2 Hz, 2H), 7.57 (t, J = 7.0 Hz, 1H), 7.51 (t, J = 7.2 Hz, 1H), 7.40 (d, J = 7.2 Hz, 2H), 7.32 (t, J = 7.4 Hz, 1H), 7.24− 7.11 (m, 4H), 5.15 (d, J = 10.0 Hz, 1H), 4.22 (dq, J = 9.7, 7.1 Hz, 1H), 2.31 (s, 3H), 1.80 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.7, 144.8, 135.8, 135.4, 134.8, 132.4, 132.2, 130.0, 129.6, 129.5, 129.3, 129.2, 128.8, 128.4, 128.2, 127.6, 126.6, 124.4, 60.2, 46.6, 21.5, 15.1; HRMS (ESI-FT-ICR) m/z: calcd for [C27H24NaO3SSe, M + Na]+, 531.0504; found, 531.0500; optical rotation: [α]20 D −42.6° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 85:15, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 15.898 min (minor), tR = 21.068 min (major). (2R,3S)-1-(Furan-2-yl)-2-(phenylselanyl)-3-tosylbutan-1-one (4r). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2s (0.1 mmol, 13.6 mg) gave compound 4r (32.0 mg, 72% yield) as a white solid with an excellent diastereomeric ratio; mp 111−113 °C; 1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 8.1 Hz, 2H), 7.53−7.45 (m, 3H), 7.34 (t, J = 7.3 Hz, 1H), 7.30−7.20 (m, 4H), 7.05 (d, J = 3.5 Hz, 1H), 6.50 (d, J = 3.3 Hz, 1H), 4.83 (d, J = 10.6 Hz, 1H), 4.08 (dq, J = 10.5, 7.1 Hz, 1H), 2.38 (s, 3H), 1.68 (d, J = 7.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 182.1, 150.8, 146.0, 144.9, 135.7, 134.6, 129.6, 129.3, 129.1, 128.9, 127.2, 117.6, 112.5, 59.6, 46.4, 21.6, 14.8; HRMS (ESI-FT-ICR) m/z: calcd for [C21H20NaO4SSe, M + Na]+, 471.0140; found, 471.0142; optical rotation: [α]20 D −87.4° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 9.682 min (minor), tR = 17.633 min (major). (2R,3S)-2-(Phenylselanyl)-1-(thiophen-2-yl)-3-tosylbutan-1-one (4s). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2t (0.1 mmol, 15.2 mg) gave compound 4s (31.0 mg, 67% yield) as a yellow solid with an excellent diastereomeric ratio; mp 124−125 °C; 1H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 4.8 Hz, 1H), 7.47−7.41 (m, 3H), 7.32 (t, J = 7.2 Hz, 1H), 7.23 (dt, J = 21.8, 6.0 Hz, 4H), 7.01 (t, J = 4.3 Hz, 1H), 4.79 (d, J = 10.0 Hz, 1H), 4.14−4.05 (m, 1H), 2.35 (s, 3H), 1.72 (d, J = 7.1 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 186.0, 144.8, 142.1, 135.6, 134.4, 133.9, 131.7, 129.5, 129.2, 129.1, 128.7, 127.8, 127.3, 59.9, 47.4, 21.4, 14.7; HRMS (ESI-FT-ICR) m/z: calcd for [C21H20NaO3S2Se, M + Na]+, 486.9911; found, 486.9913; optical rotation: [α] D20 −120.9° (c = 1.0, CHCl3 ); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 19.253 min (major), tR = 32.079 min (minor). (2R,3S)-1,5-Diphenyl-2-(phenylselanyl)-3-tosylpentan-1-one (4t). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2u (0.1 mmol, 23.6 mg) gave compound 4t (26.8 mg, 49% yield) as a white solid with an excellent diastereomeric ratio; mp 87−88 °C; 1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 7.6 Hz, 2H), 7.64 (d, J = 7.7 Hz, 2H), 7.52 (t, J = 7.3 Hz, 1H), 7.37 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 6.7 Hz, 3H), 7.26 (d, J = 7.7 Hz, 2H), 7.24− 7.08 (m, 7H), 5.14 (d, J = 10.0 Hz, 1H), 4.20−4.11 (m, 1H), 2.97−2.79 (m, 2H), 2.75−2.65 (m, 1H), 2.60−2.49 (m, 1H), 2.37 (s, 3H);

C{1H} NMR (100 MHz, CDCl3): δ 193.0, 144.8, 140.8, 136.1, 135.6, 135.5, 132.9, 129.7, 129.3, 129.2, 128.6, 128.6, 128.5, 128.4, 127.5, 126.1, 63.8, 46.5, 33.4, 31.2, 21.6; HRMS (ESI-FT-ICR) m/z: calcd for [C30H28NaO3SSe, M + Na]+, 571.0817; found, 571.0814; optical rotation: [α]20 D −42.7° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 75:25, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 11.787 min (major), tR = 26.571 min (minor). (2R,3S)-1-Phenyl-2-(phenylselanyl)-3-tosylpentan-1-one (4u). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2v (0.1 mmol, 16.0 mg) gave compound 4u (21.5 mg, 46% yield) as a white solid with an excellent diastereomeric ratio; mp 107−108 °C; 1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 7.7 Hz, 2H), 7.64 (d, J = 8.1 Hz, 2H), 7.52 (t, J = 7.3 Hz, 1H), 7.38 (t, J = 7.9 Hz, 4H), 7.32 (d, J = 7.2 Hz, 1H), 7.22 (dd, J = 12.8, 7.7 Hz, 4H), 5.09 (d, J = 10.1 Hz, 1H), 4.05−3.98 (m, 1H), 2.51−2.43 (m, 1H), 2.37 (s, 3H), 2.34−2.27 (m, 1H), 1.59 (s, 3H), 1.14 (t, J = 7.4 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 193.0, 144.6, 136.4, 135.6, 135.5, 132.8, 129.6, 129.2, 129.2, 128.5, 128.4, 128.3, 127.4, 65.7, 46.2, 22.6, 21.5, 12.0; HRMS (ESI-FT-ICR) m/z: calcd for [C24H24NaO3SSe, M + Na]+, 495.0504; found, 495.0500; optical rotation: [α]D20 −110.6° (c = 1.0, CHCl 3 ); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 90:10, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 29.349 min (major), tR = 31.315 min (minor). (2R,3S)-4-Hydroxy-1-phenyl-2-(phenylselanyl)-3-tosylbutan-1one (4v). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2w (0.1 mmol, 16.2 mg) gave compound 4v (19.9 mg, 42% yield) as a yellow solid with an excellent diastereomeric ratio; mp 81−82 °C; 1H NMR (400 MHz, CDCl3): δ 7.83 (d, J = 7.6 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.51 (t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.4 Hz, 4H), 7.31 (d, J = 7.1 Hz, 1H), 7.25−7.17 (m, 4H), 5.24 (d, J = 11.2 Hz, 1H), 4.63−4.49 (m, 2H), 4.15−4.08 (m, 1H), 3.42 (s, 1H), 2.34 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 192.2, 145.1, 136.2, 135.7, 135.2, 132.9, 129.8, 129.4, 129.1, 128.5, 128.3, 126.7, 66.2, 60.3, 42.9, 21.5; HRMS (ESI-FT-ICR) m/z: calcd for [C23H22NaO4SSe, M + Na]+, 497.0296; found, 497.0295; optical rotation: [α]D20 −107.6° (c = 1.0, CHCl 3 ); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 10.587 min (major), tR = 14.650 min (minor). (2S,3S)-2-(Phenylselanyl)-3-tosylcyclopentan-1-one (4w). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2x (0.1 mmol, 9.6 mg) gave compound 4w (8.6 mg, 21% yield) as a yellow solid with an excellent diastereomeric ratio; mp 77−80 °C; 1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.1 Hz, 2H), 7.27 (dd, J = 15.8, 7.8 Hz, 5H), 7.16 (t, J = 7.6 Hz, 2H), 3.97− 3.91 (m, 1H), 3.59−3.55 (m, 1H), 2.86−2.75 (m, 1H), 2.52−2.41 (m, 5H), 2.40−2.24 (m, 2H), 2.02−1.93 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 202.9, 145.0, 134.4, 133.9, 129.9, 129.4, 128.8, 128.5, 127.4, 66.5, 45.8, 36.5, 21.5, 21.2, 19.8; HRMS (ESI-FT-ICR) m/z: calcd for [C18H18NaO3SSe, M + Na]+, 417.0034; found, 417.0030; optical rotation: [α]20 D −64.0° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL OD-H (hexane/i-PrOH) = 85:15, flow rate = 1.0 mL/ min, wavelength = 254 nm, tR = 14.295 min (minor), tR = 15.084 min (major). (2S,3S)-2-(Phenylselanyl)-3-tosylcycloheptan-1-one (4x). According to GP-3, combining selenosulfonate 1a (0.1 mmol, 31.1 mg) and α,β-unsaturated ketone 2y (0.1 mmol, 11.0 mg) gave compound 4x (16.9 mg, 40% yield) as a white solid with an excellent diastereomeric ratio; mp 130−131 °C; 1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 7.1 Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H), 7.30 (d, J = 7.1 Hz, 1H), 7.27−7.18 (m, 2H), 3.95 (d, J = 7.2 Hz, 1H), 3.40 (td, J = 7.4, 2.4 Hz, 1H), 2.94−2.85 (m, 1H), 2.55−2.36 (m, 5H), 2.12−2.02 (m, 1H), 1.99−1.88 (m, 2H), 1.76−1.64 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3): δ 203.8, 145.3, 134.7, 134.3, 130.0, 129.3, 129.0, 128.8, 128.0, 66.2, 51.8, 40.8, 27.7, 27.3, 24.8, 21.7; HRMS (ESI-FT-ICR) m/ z: calcd for [C20H22NaO3SSe, M + Na]+, 445.0347; found, 445.0344; optical rotation: [α]20 D −44.4° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 80:20, flow rate = 1.0 mL/ 13

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DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

The Journal of Organic Chemistry

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min, wavelength = 254 nm, tR = 17.662 min (major), tR = 19.320 min (minor). Procedure for Scale-Up Experiment (P-1). In a 500 mL jacket reactor was added 300 mL sat. NaCl solution with vigorous agitation by machinery stirring. Then, a mixture of selenosulfonate 1a (20.2 g, 65.0 mmol, 1.0 equiv), substrate 2k (14.6 g, 65.0 mmol, 1.0 equiv), and catalyst D (10 mmol %) was added into the reaction mixture in portion. After stirring vigorously at 25 °C for 2 h, 200 mL CH3CN was added and stirred for 20 min. The reaction mixture was standing for 15 min. The aqueous layer was separated, and the organic layer was filtered to give 4j (28.2 g, 81% yield) as a white solid with 87% ee. Procedure for the Synthesis of 5 (P-2). 4j (53.6 mg, 96% ee, 0.1 mmol, 1.0 equiv) and CeCl3·7H2O (74.5 mg, 0.2 mmol, 2.0 equiv) were added into a 10 mL tube, CH3OH (1 mL) was introduced, and then the mixture was cooled down to 0 °C. NaBH4 (0.2 mmol, 2.0 equiv) was added in portion. The reaction mixture was stirred for 2 h at 0 °C, then quenched by H2O, extracted with ethyl acetate, washed with brine, dried over Na2SO4 and filtered, concentrated under reduced pressure, and purified by column chromatography (SiO2, PE/EA = 6:1) to afford 5 as a white solid (74% yield, 93% ee). (1S,2R,3S)-1-(4-Bromophenyl)-2-(phenylselanyl)-3-tosylbutan-1ol (5). This product was prepared according to P-2; 5 (39.8 mg, 74% yield) was afforded as a white solid; mp 151−152 °C; 1H NMR (600 MHz, CDCl3): δ 7.51 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 8.3 Hz, 2H), 7.30 (d, J = 7.3 Hz, 2H), 7.23 (d, J = 8.1 Hz, 3H), 7.16 (dd, J = 12.7, 7.9 Hz, 4H), 5.15 (t, J = 4.5 Hz, 1H), 3.71 (t, J = 5.0 Hz, 1H), 3.42−3.37 (m, 1H), 3.36 (d, J = 4.2 Hz, 1H), 2.42 (s, 3H), 1.40 (d, J = 7.0 Hz, 3H); 13 C{1H} NMR (150 MHz, CDCl3): δ 144.8, 140.0, 134.5, 134.2, 131.2, 129.7, 129.5, 129.0, 128.6, 128.1, 127.7, 121.7, 74.1, 61.7, 56.8, 21.6, 14.3; HRMS (ESI-FT-ICR) m/z: calcd for [C23H23NaBrO3SSe, M + Na]+, 560.9609; found, 560.9608; optical rotation: [α]20 D 15.6° (c = 1.0, CHCl3); HPLC analysis: CHIRALCEL AD-H (hexane/i-PrOH) = 70:30, flow rate = 1.0 mL/min, wavelength = 254 nm, tR = 10.820 min (minor), tR = 16.343 min (major).

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.9b00973. Crystal data for 4u (CIF) Crystal data for 4x (CIF) Crystal data for 5 (CIF) 1

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Article

H NMR and 13C NMR spectra of new compounds and crystallographic data of 4u, 4x, and 5 (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (H.M.). *E-mail: [email protected] (W.Q.). ORCID

Wenling Qin: 0000-0002-5654-5785 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This study was supported by Fundamental Research Funds for the Central Universities (2018CDYXYX0027), Chongqing Science and Technology Commission (grant no.: cstc2017zdcyadyfX0022), and Zhejiang Provincial Natural Science Foundation of China (LQ19B020003). H.M. thanks the support from Jinhua Science and Technology Bureau (20184-105). 8110

DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111

Article

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DOI: 10.1021/acs.joc.9b00973 J. Org. Chem. 2019, 84, 8100−8111