Diasteroselective and Enantioselective Ir-Catalyzed Allylic

Sep 6, 2017 - Diasteroselective and Enantioselective Ir-Catalyzed Allylic Substitutions of 1-Substituted 1-Fluoro-1-(arenesulfonyl)methylene Derivativ...
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Diasteroselective and Enantioselective Ir-Catalyzed Allylic Substitutions of 1‑Substituted 1‑Fluoro-1-(arenesulfonyl)methylene Derivatives Jiteng Chen,†,‡ Xiaoming Zhao,*,†,‡ and Wenyan Dan†,‡ †

Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Technology and Engineering, Tongji University, 1239 Siping Road, 200092 Shanghai, P. R. China ‡ Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. China S Supporting Information *

ABSTRACT: diasteroselective and enantioselective Ir-catalyzed allylic substitutions of 1-substituted 1-fluoro-1(arenesulfonyl)methylene derivatives are presented, which afford the fluorinated allyl products with two chirality centers. The steric demand of 1-substituted 1-fluoro-1-(arenesulfonyl)methylene derivatives and allylic substrates has a great influence on the dr values of these reactions. The transformation of the branched allyl product into the fluorinated 3,4dihydro-2H-pyrrole 1-oxide was discussed, as well. he enantioselective introduction of a fluorinated methylene group into organic molecules could dramatically enhance their physicochemical and biological properties;1 for example, popular drugs2 such as clevudine,2a,b clofarabine,2c fluticasone furoate,2d and difluprednate2e contain a chiral carbon-fluorinated carbon fragment (Figure S1). A strategy for the enantioselective incorporation of a fluorinated methylene unit into organic molecules is by transition-metalcatalyzed asymmetric allylic substitution of fluorinated methylene derivatives.3 In this regard, fluorinated methylene derivatives including fluorobisphenylsulfonylmethane4 and 2fluoromalonate 5 were applied in Pd-6 or Ir7-catalyzed asymmetric allylation reactions in which a chiral carbonfluorinated carbon center was formed. However, racemic fluorinated methylene derivatives, which afford the allyl products with two chiral centers, have been less investigated. Notably, it is challenging to control the stereochemistry of this type of reactions.8 In addition, the fluorinated allyl products are of great importance for the synthesis of high value-adding compounds.9 To the best of our knowledge, Ir-catalyzed allylic substitution of racemic fluorinated methylene derivatives is hardly reported. In this paper, we report Ir-catalyzed allylic substitutions of 1-substituted 1-fluoro-1-(arenesulfonyl)methylene derivatives, which give the allyl products with two chiral centers. We started our investigation with a reaction of (E)-cinnamyl methyl carbonate 1a with diverse racemic fluorinated methylene derivatives in the presence of an iridacycle7a,d made from [Ir(COD)Cl]2 and Feringa’s ligand L1 in DCM at room temperature. After a series of experiments, we found that methyl 2-fluoro-2-(phenylsulfonyl)acetate 2a gave the allylic product 3a with increasing dr in comparison with ethyl 2fluoro-3-oxobutanoate 2e, which gave the corresponding allyl

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© 2017 American Chemical Society

product with no diasteroselectivity.8b As a result, 2a was employed for further investigation. The nature of bases has a considerable impact on the result of Ir-catalyzed allylic substitution;7 the subsequent examination of bases such as Cs2CO3, CsF, K2CO3, and K3PO4 revealed that K3PO4 gave superior results, 85% yield with 99% ee, b/l 99/1, and dr 4.3/1 (Table 1, entry 4). The other bases provided somewhat lower dr and yields (Table 1, entries 1−3). A solvent survey indicated that the use of DCM offered the highest efficiency, regioselectivity, and enantioselectivity but moderate diastereoselectivity; the use of MeCN and THF gave lower dr and yields but maintained excellent regio- and enantioselectivities (entries 6 and 7). Toluene is not effective for this reaction (entry 5). The other iridium species including [Ir(Cp*)Cl]2 and [Ir(dba)3] were also explored, and they are not able to catalyze this reaction (entries 8 and 9). Next, a range of chiral ligands including Feringa’s L1, L2, L3, and L4 were evaluated (Figure 1). The use of L1 offered the best result (entry 3); L2, with two bulky 2-naphthyl groups, gave rise to 3a in a decreasing yield with high regio- and enantioselectivity but fair diastereoselectivity (entry 4 vs entry 10). L3, with a less steric phenyl ring, and L4, with a 2-methylpiperidinyl group, failed to promote this reaction, presumably due to their mismatched effect on this reaction (entries 11 and 12). Variation of the reaction temperature has a considerable impact on the efficiency and stereoselectivities of this reaction (entries 4, 13, and 14). Once we established that the iridacycle7a,d catalyzed the diastereo- and enantioselective allylation efficiently, the scope Received: July 18, 2017 Published: September 6, 2017 10693

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698

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The Journal of Organic Chemistry Table 1. Optimization of Reaction Conditions for an Ir-Catalyzed Allylic Substitution of 2aa

entry

L

sol

temp (°C)

base

yieldb (%) of 3a

3a/4ac

eed (%)

dre

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

L1 L1 L1 L1 L1 L1 L1 L1 L1 L2 L3 L4 L1 L1

DCM DCM DCM DCM toluene MeCN THF DCM DCM DCM DCM DCM DCM DCM

25 25 25 25 25 25 25 25 25 25 25 25 0 35

Cs2CO3 CsF K2CO3 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4 K3PO4

51 31 48 86 trace 37 14 nrh nr 68 nr nr 47 83

99/1 99/1 99/1 99/1

93 98 99

3/1 3.5/1 2.7/1 4.3/1

99/1 99/1

95 96

2.5/1 2/1

99/1

98

3.5/1

99/1 99/1

99 96

3.5/1 3.5/1

Reaction conditions: 2 mol % of [Ir(COD)Cl]2, 4 mol % of L, 1a (0.1 mmol), and 2a (0.2 mmol) in solvent (2 mL) at 0−35 °C for 12 h. bIsolated yields were reported as the combined yield of two diastereoisomers. cDetermined by 1H NMR. dDetermined by chiral HPLC. eDetermined by 19F NMR of the crude product. f[Ir(Cp*)Cl]2 was used. g[Ir(dba)3] was used. hnr = no reaction. a

Figure 1. Chiral ligands L1−L4 used in the present reaction.

as well. An alkyl-substituted allylic substrate such as 1k was also examined, and it gave 3k in a 70% yield and 96% ee with b/l 99/1 and 1/1 dr. After recrystallization from ethyl acetate, the fluorinated compound 3c in enantiopure form was obtained. Therefore, the absolute configuration of the compound 3c is recognized as (R,R) by means of its X-ray diffraction analysis (Figure S2).10 A large-scale synthesis of the branched allylproduct 3c was also exploited as demonstrated in Scheme 1. For example, the allylation reaction of the allylic substrate 1c (638 mg, 2.50 mmol) with methyl 2-fluoro-2-(phenylsulfonyl)acetate 2a (870 mg, 3.75 mmol) underwent under the optimized conditions, and it provided the branched allyl product 3c in a 62% yield with b/1 99/1, 99% ee, and dr 3.7/1 (Scheme 1). The introduction of a fluorine atom into drug molecules can enhance their lipophilicity and metabolic stability.11 Therefore, the transformation of the branched fluorinated allyl product 3c into the fluorinated 3,4-dihydro-2H-pyrrole 1-oxide 7a was also investigated (Scheme 1). After recrystallization, the dr value of 3c was improved from 3.7/1 to >20/1. The reduction of 3c (99% ee and dr >20/1) with DIBAL-H in toluene at −78 °C gave the corresponding product 5a in a 85% yield with 98% ee and dr >20/1. The cyclization of 5a in the presence of hydroxylamine hydrochloride (NH2OH·HCl), triethylamine (TEA), and DCM proceeded at room temperature to give the fluorinated 4H-1,2-oxazine 6a, which is also in accord with the known work,6e and then a rearrangement reaction of 6a occurred in one pot to form 3,4-dihydro-2H-pyrrole 1-oxide

of the reaction between the allylic substrates 1 and 1substituted 1-fluoro-1-(arenesulfonyl)methylene derivatives 2 was subsequently examined. Use of methyl 2-fluoro-2(phenylsulfonyl)acetate 2a, (E)-cinnamyl methyl carbonate 1a, and the substrate 1b,c with a substituent (e.g., Ph and Br) at the 4-position on the phenyl ring afforded the corresponding 3a−c with 76−98% yield and 3.7/1−4.3/1 dr. The substrate 1d−f with a substituent (e.g., Me, F, and CF3) at the 3-position furnished 3d−f in 61−95% yield with 4.5/1−5.1/1 dr (Table 2). The substrate 1d−f gave a slightly higher dr than that of 1a−1c. 2-Naphthyl-substituted allylic acetate 1g produced 3g in a 83% yield with b/l 99/1, 96% ee, and 3.6/1 dr (Table 2). These results also suggested that the dr values are governed by the steric demand of the substituent on the phenyl ring of the allylic substrates. When 2b was used, which replaced CO2Me with NO2 in 2a, the allylic substrate 1g was tested, and it led to the corresponding 3h with a somewhat lower dr (Table 2). The allylic product 3h could be converted into fluorinated β-amino acids by tandem reduction of NO2 and ozone oxidation of a terminal alkene.3a It is noteworthy that all of the substrates 1a− g led to the corresponding 3a−h with excellent regio- and enantioselectivities (Table 2). Furthermore, the fluorinated methylene derivatives 2c,d possessing a bulky sulfonyl group (e.g., 2-NpSO2 and 3-MeOC6H4SO2) were employed, and they provided the corresponding 3i and 3j with slightly lower ee and dr (Table 2). These results indicated that the further increased steric demand of the sulfonyl group has a somewhat negative effect on the enantio- and diastereoselectivities of this reaction, 10694

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698

Note

The Journal of Organic Chemistry Table 2. Nucleophiles and Substrate Scopea−e

Reaction conditions: 2 mol % of [Ir(COD)Cl]2, 4 mol % of L1, 1a (0.1 mmol), and 2a (0.2 mmol) in DCM (2 mL) at 25 °C for 12 h. bIsolated yields were reported as the combined yield of two diastereoisomers. c3/4 was determined by 1H NMR. dee was determined by chiral HPLC. edr was determined by 19F NMR. a

Scheme 1. Application of the Branched Compound 3c in the Synthesis of Cyclic Compound 7a

synthesize the fluorinated allylproducts with two chiral carbon−carbon centers.

7a12 in 80% yield with 97% ee and dr >20/1 (Scheme 1 and Figure S3). In summary, we have developed a diasteroselective and enantioselective Ir-catalyzed allylic substitution of 1-substituted 1-fluoro-1-(arenesulfonyl)methylene derivatives, which gives the allylic products with high diastereo- and enantioselectivities in one pot. This method allows the use of 1-substituted 1fluoro-1-(arenesulfonyl)methylene derivatives, tolerates various aryl-substituted substrates, and provides a new way to

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EXPERIMENTAL SECTION

General Methods. All manipulations were carried out under air atmosphere using standard Schlenk techniques. All glassware was oven or flame-dried immediately prior to use. All solvents were purified and dried according to standard methods prior to use, unless stated otherwise. All reagents were obtained from commercial sources, most of them from Adamas-beta and used without further purification. 1H NMR spectra were obtained at 400 MHz and recorded relative to the 10695

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698

Note

The Journal of Organic Chemistry tetramethylsilane signal (0 ppm) or residual protio-solvent. 13C NMR spectra were obtained at 100 MHz, and chemical shifts were recorded relative to the solvent resonance (CDCl3, 77.0 ppm). 19F NMR spectra were obtained at 376 MHz. Infrared (IR) spectra were recorded on an IR spectrometer with KBr wafers or a film on KBr plate. Highresolution mass spectra (HRMS) were recorded on a micrOTOF II mass spectrometer using electrospray ionization (ESI). Data collections for crystal structures were performed at room temperature (293 K) or 150 K using an X-ray single-crystal diffractometer (D8 VENTURE). Melting point temperatures were measured at a heating rate of 5 °C/min and are uncorrected. Data for 1H NMR are recorded as follows: chemical shift (δ, ppm), multiplicity (s = singlet, d = doublet, t = triplet, m = multiplet or unresolved, br = broad singlet, coupling constant(s) in Hz, integration). Data for 13C NMR are reported in terms of chemical shift (δ, ppm). The 4,6-disubstituted pyrimidin-2-amines were prepared according to the known procedures. General Procedure for the Synthesis of 3a−p. [Ir(COD)Cl]2 (0.004 mmol, 2 mol %) and phosphoramidite ligand L1 (0.008 mmol, 4 mol %) were dissolved in THF (0.5 mL) and propylamine (0.3 mL) in a dry Schlenk tube filled with argon. The reaction mixture was heated at 50 °C for 30 min, and then the volatile solvents were removed under vacuum to give a yellow solid. After that, allylic carbonate 1 (0.20 mmol), fluorinated phenylsulfonyl methylene 2 (0.30 mmol, 150 mol %), potassium phosphate (0.40 mmol, 200 mol %), and DCM (2.0 mL) were added. The reaction was stirred at room temperature until the carbonate was fully consumed and monitored by TLC or 1H NMR. Then the crude reaction mixture was filtrated with Celite, and the solvent was removed under reduced pressure. The ratio of regioisomers (branched to linear b/l) was determined by 1H NMR of the crude reaction mixture. The crude residue was purified by flash column chromatography (petroleum ether/ethyl acetate) to give the desired product 3. Methyl (2R,3R)-2-Fluoro-3-phenyl-2-(phenylsulfonyl)pent-4enoate (3a). White solid. Mp: 59−71 °C; 86% yield (59.8 mg); 99% ee [Daicel CHIRALCEL IC (0.46 cm × 25 cm); n-hexane/2propanol = 90/10; flow rate = 1.0 mL/min; detection wavelength = 214 nm; tR = 14.68 (major), 15.33 (minor), 18.06 (major), 22.41 (minor) min]. [α]D20 = −112.0 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.1 Hz, 7H), 7.70 (t, J = 7.4 Hz, 4H), 7.61− 7.40 (m, 10H), 7.21−7.15 (m, 2H), 6.35−6.16 (m, 4H), 6.02 (dt, J = 17.0, 9.7 Hz, 1H), 5.33 (dd, J = 21.2, 13.6 Hz, 7H), 5.22 (dd, J = 25.0, 13.5 Hz, 2H), 4.68 (dd, J = 32.8, 8.7 Hz, 4H), 4.55 (dd, J = 33.0, 9.3 Hz, 1H), 3.84 (s, 3H), 3.33 (s, 10H). 19F NMR (376 MHz, CDCl3): δ −162.08 (s), −164.28 (s). 13C NMR (101 MHz, CDCl3): δ 163.7 (d, J = 5.8 Hz), 163.43 (s), 136.8 (s), 135.6 (s), 134.9 (d, J = 14.6 Hz), 134.2 (s), 133.8 (d, J = 3.6 Hz), 132.3 (d, J = 5.2 Hz), 130.4 (d, J = 0.6 Hz), 130.0 (d, J = 2.0 Hz), 129.1−128.4 (m), 128.0 (d, J = 2.9 Hz), 120.5 (s), 119.7 (s), 110.2 (s), 107.8 (s), 53.8 (s), 53.1 (s), 52.6 (d, J = 17.0 Hz), 51.8 (d, J = 17.2 Hz). IR (KBr): νmax (cm−1) = 3006, 2919, 2848, 2350, 1769, 1644, 1275, 1161, 763, 749. HRMS (ESI-TOF): calcd for C18H17FNaO4S [M + Na]+ 371.0723, found 371.0724. Methyl (2R,3R)-3-([1,1′-Biphenyl]-4-yl)-2-fluoro-2(phenylsulfonyl)pent-4-enoate (3b). White solid. Mp: 109−123 °C; 98% yield (83.1 mg); 98% ee [Daicel CHIRALCEL IC (0.46 cm × 25 cm); n-hexane/2-propanol = 90/10; flow rate = 0.4 mL/min; detection wavelength = 214 nm; tR = 62.01 (minor), 64.57 (major), 72.76 (major), 111.46 (minor) min]. [α]D20 = −112.3 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 7.1 Hz, 6H), 7.70 (t, J = 6.7 Hz, 4H), 7.62−7.18 (m, 48H), 6.36−6.20 (m, 3H), 6.11−5.95 (m, 1H), 5.36 (dd, J = 27.8, 14.3 Hz, 7H), 5.30−5.16 (m, 2H), 4.74 (dd, J = 32.5, 8.1 Hz, 3H), 4.60 (dd, J = 33.8, 9.8 Hz, 1H), 3.89 (s, 2H), 3.37 (s, 9H). 19F NMR (377 MHz, CDCl3): δ −162.11 (s), −164.22 (s). 13C NMR (101 MHz, CDCl3): δ 163.7 (s), 163.5 (s), 140.9 (d, J = 11.5 Hz), 140.3 (s), 135.7 (d, J = 13.2 Hz), 135.0 (s), 134.0 (s), 133.8 (d, J = 20.0 Hz), 132.3 (d, J = 5.1 Hz), 130.4 (s), 130.0 (s), 129.0 (dd, J = 22.2, 8.3 Hz), 128.5 (s), 127.5 (s), 127.2 (s), 127.0 (s), 120.6 (s), 119.8 (s), 107.8 (s), 53.9 (s), 53.2 (s), 52.4 (d, J = 16.8 Hz), 51.5 (d, J = 17.2 Hz). IR (KBr): νmax (cm−1) = 3005, 2918, 2848, 2348, 1768, 1747, 1646, 1331, 1274, 1162, 763, 749, 598. HRMS

(ESI-TOF): calcd for C24H25FNO4S [M + NH4]+ 442.1483, found 442.1484. Methyl (2R,3R)-3-(4-Bromophenyl)-2-fluoro-2-(phenylsulfonyl)pent-4-enoate (3c). White solid. Mp: 64−66 °C; 76% yield (64.8 mg), 99% ee [Daicel CHIRALCEL IC (0.46 cm × 25 cm); n-hexane/ 2-propanol = 90/10; flow rate = 0.6 mL/min; detection wavelength = 214 nm; tR = 28.80 (major), 29.81 (minor), 32.70 (major), 42.00 (minor) min]. [α]D20 = −120.0 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.1 Hz, 6H), 7.71 (t, J = 7.5 Hz, 3H), 7.57 (t, J = 7.8 Hz, 7H), 7.46 (d, J = 8.2 Hz, 2H), 7.41 (d, J = 8.4 Hz, 5H), 7.32 (dd, J = 20.9, 12.0 Hz, 6H), 7.13 (d, J = 7.5 Hz, 7H), 6.21 (ddd, J = 17.1, 10.0, 8.8 Hz, 3H), 5.95 (dt, J = 17.0, 9.6 Hz, 1H), 5.32 (dd, J = 13.6, 6.1 Hz, 6H), 5.28−5.17 (m, 2H), 4.66 (dd, J = 32.4, 8.6 Hz, 3H), 4.53 (dd, J = 32.8, 9.1 Hz, 1H), 3.83 (s, 3H), 3.36 (s, 9H). 19F NMR (376 MHz, CDCl3): δ −162.70 (s), −164.52 (s). 13C NMR (101 MHz, CDCl3): δ 163.5 (d, J = 24.9 Hz), 135.8 (s), 135.4 (s), 135.1 (s), 134.40 (s), 132.2−131.6 (m), 130.6−130.3 (m), 129.93 (s), 129.1 (s), 128.7 (s), 122.3 (s), 120.9 (s), 120.2 (s), 109.8 (s), 107.4 (s), 53.9 (s), 53.3 (s), 51.9 (d, J = 16.9 Hz), 51.1 (d, J = 17.3 Hz). IR (KBr): νmax (cm−1) = 3006, 2919, 2848, 2348, 1766, 1746, 1488, 1275, 1260, 764, 750, 600. HRMS (ESI-TOF): calcd for C18H16BrFNaO4S [M + Na]+ 448.9814, found 448.9826. Methyl (2R,3R)-2-Fluoro-2-(phenylsulfonyl)-3-(m-tolyl)pent-4enoate (3d). Colorless oil; 61% yield (44.2 mg); 96% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/ 10; flow rate = 0.8 mL/min; detection wavelength = 214 nm; tR = 12.09 (major), 13.11 (minor), 17.93 (major), 23.33 (minor) min]. [α]D20 = −55.6 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 8.0 Hz, 7H), 7.69 (t, J = 7.4 Hz, 4H), 7.56 (t, J = 7.8 Hz, 7H), 7.45 (dd, J = 31.9, 7.7 Hz, 3H), 7.31−7.24 (m, 3H), 7.15 (t, J = 7.5 Hz, 4H), 7.04 (d, J = 9.6 Hz, 14H), 6.23 (dt, J = 17.2, 9.6 Hz, 4H), 5.99 (dt, J = 17.0, 9.7 Hz, 1H), 5.32 (dd, J = 26.4, 13.6 Hz, 8H), 5.20 (dd, J = 26.5, 13.5 Hz, 2H), 4.63 (dd, J = 32.9, 8.8 Hz, 4H), 4.49 (dd, J = 33.1, 9.3 Hz, 1H), 3.86 (s, 3H), 3.35 (s, 11H), 2.29 (s, 11H), 2.18 (s, 3H). 19F NMR (377 MHz, CDCl3): δ −161.80 (s), −164.10 (s). 13C NMR (101 MHz, CDCl3): δ 163.7 (d, J = 3.7 Hz), 163.4 (s), 138.5 (s), 138.2 (s), 136.7 (s), 135.7 (s), 135.3 (s), 135.0 (s), 134.7 (s), 134.0 (d, J = 17.8 Hz), 132.4 (d, J = 5.3 Hz), 130.7−130.3 (m), 130.1 (d, J = 1.8 Hz), 129.4 (d, J = 2.0 Hz), 129.0 (s), 128.9−128.7 (m), 128.4 (d, J = 13.2 Hz), 127.1 (s), 125.7 (d, J = 2.0 Hz), 120.3 (s), 119.5 (s), 110.3 (s), 107.9 (s), 53.8 (s), 53.1 (s), 52.7 (d, J = 16.9 Hz), 51.7 (d, J = 17.1 Hz), 21.4 (d, J = 11.2 Hz). IR (KBr): νmax (cm−1) = 3066, 2919, 2849, 2348, 1767, 1642, 1447, 1336, 1159, 1135, 715,705. HRMS (ESI-TOF): calcd for C19H19FNaO4S [M + Na]+ 385.0878, found 385.0880. Methyl (2R,3R)-2-Fluoro-3-(3-fluorophenyl)-2-(phenylsulfonyl)pent-4-enoate (3e). Colorless oil; 95% yield (69.5 mg); 99% ee [Daicel CHIRALCEL IC (0.46 cm × 25 cm); n-hexane/2-propanol = 90/10; flow rate = 0.6 mL/min; detection wavelength = 214 nm; tR = 25.89 (major), 27.01 (minor), 33.39 (major), 38.38 (minor) min]. [α]D20 = −70.0 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 8.2 Hz, 7H), 7.71 (t, J = 7.5 Hz, 4H), 7.57 (t, J = 7.8 Hz, 9H), 7.50 (d, J = 8.3 Hz, 2H), 7.35 (t, J = 7.9 Hz, 2H), 7.29−7.14 (m, 6H), 7.11−6.89 (m, 14H), 6.21 (ddd, J = 17.1, 10.0, 8.9 Hz, 4H), 5.97 (dt, J = 16.9, 9.7 Hz, 1H), 5.35 (t, J = 13.9 Hz, 7H), 5.24 (dd, J = 18.7, 13.5 Hz, 2H), 4.69 (dd, J = 32.2, 8.7 Hz, 4H), 4.56 (dd, J = 32.3, 9.3 Hz, 1H), 3.82 (s, 3H), 3.37 (s, 11H). 19F NMR (376 MHz, CDCl3): δ −111.84 (s), −112.61 (s), −162.41 (s), −164.38 (s). 13C NMR (101 MHz, CDCl3): δ 164.0−163.2 (m), 161.4 (d, J = 10.4 Hz), 139.0 (d, J = 7.3 Hz), 137.2 (d, J = 7.5 Hz), 135.4 (s), 135.1 (s), 134.5 (s), 133.2 (s), 131.8 (d, J = 5.1 Hz), 130.4 (d, J = 5.7 Hz), 130.0 (d, J = 7.9 Hz), 129.1 (s), 128.6 (s), 125.8 (s), 124.4 (s), 121.0 (s), 120.2 (s), 116.9 (s), 116.7 (s), 115.8 (dd, J = 22.3, 2.3 Hz), 115.1 (dd, J = 21.0, 6.9 Hz), 109.9 (s), 107.4 (s), 53.8 (s), 53.2 (s), 52.1 (d, J = 18.6 Hz), 51.4 (d, J = 15.7 Hz). IR (KBr): νmax (cm−1) = 3006, 2919, 2848, 2348, 1767, 1746, 1644, 1589, 1488, 1448, 1274, 1259, 1162, 763, 750. HRMS (ESI-TOF): calcd for C18H16F2NaO4S [M + Na]+ 389.0639, found 389.0630. Methyl (2R,3R)-2-Fluoro-2-(phenylsulfonyl)-3-(3(trifluoromethyl)phenyl)pent-4-enoate (3f). Colorless oil; 62% yield 10696

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698

Note

The Journal of Organic Chemistry (51.6 mg); 96% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm). nhexane/2-propanol = 90/10; flow rate = 0.6 mL/min; detection wavelength = 214 nm; tR = 14.91 (major), 15.66 (minor), 29.28 (major), 34.87 (minor) min]; [α]D20 = −54.4 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.93 (d, J = 7.7 Hz, 7H), 7.71 (t, J = 7.3 Hz, 4H), 7.62−7.39 (m, 27H), 7.35−7.23 (m, 4H), 6.35−6.17 (m, 4H), 6.05−5.92 (m, 1H), 5.45−5.31 (m, 8H), 5.31−5.19 (m, 2H), 4.77 (dd, J = 32.1, 8.6 Hz, 4H), 4.63 (dd, J = 32.3, 9.1 Hz, 1H), 3.86 (s, 3H), 3.34 (s, 11H). 19F NMR (377 MHz, CDCl3): δ −62.64 (s), −62.73 (s), −162.42 (s), −164.42 (s). 13C NMR (101 MHz, CDCl3): δ 137.8 (s), 135.4 (s), 135.2 (s), 132.2 (s), 131.7−131.3 (m), 131.0 (s), 130.4 (s), 129.9 (s), 129.4 (s), 129.1 (d, J = 8.1 Hz), 128.6 (s), 125.6 (s), 124.9 (s), 121.4 (s), 53.2 (s), 51.5 (d, J = 17.4 Hz). IR (KBr): νmax (cm−1) = 3006, 2919, 2848, 2348, 1768, 1748, 1644, 1330, 1275, 1260, 1162, 1128, 764, 749. HRMS (ESI-TOF): calcd for C19H16F4NaO4S [M + Na]+ 439.0595, found 439.0598. Methyl (2R,3R)-2-Fluoro-3-(naphthalen-2-yl)-2-(phenylsulfonyl)pent-4-enoate (3g). White solid. Mp: 61−67 °C; 83% yield (66.0 mg); 96% ee [Daicel CHIRALCEL IC (0.46 cm × 25 cm); n-hexane/ 2-propanol = 90/10; flow rate = 0.8 mL/min; detection wavelength = 214 nm; tR = 29.91 (minor), 32.54 (major), 36.47 (major), 48.68 (minor) min]. [α]D20 = −121.4 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 8.1 Hz, 7H), 7.72 (ddd, J = 16.4, 11.6, 6.2 Hz, 20H), 7.57 (t, J = 12.9 Hz, 8H), 7.45 (dd, J = 6.4, 3.1 Hz, 9H), 7.37 (d, J = 8.6 Hz, 4H), 7.28 (dd, J = 18.3, 7.2 Hz, 5H), 6.94 (t, J = 7.9 Hz, 2H), 6.35 (ddd, J = 17.2, 10.0, 8.8 Hz, 3H), 6.10 (dt, J = 17.0, 9.6 Hz, 1H), 5.35 (dd, J = 22.2, 13.6 Hz, 7H), 5.31−5.17 (m, 2H), 4.87 (dd, J = 32.8, 8.6 Hz, 3H), 4.71 (dd, J = 33.1, 9.2 Hz, 1H), 3.89 (s, 3H), 3.27 (s, 10H). 19F NMR (377 MHz, CDCl3): δ −161.84 (s), −163.87 (s). 13 C NMR (101 MHz, CDCl3): δ 164.0 (s), 163.7 (s), 163.5 (s), 135.6 (s), 135.1 (s), 134.3 (s), 134.0 (s), 133.7 (d, J = 3.5 Hz), 133.3 (d, J = 13.6 Hz), 132.9 (d, J = 9.6 Hz), 132.3 (t, J = 12.1 Hz), 130.4 (s), 129.9 (d, J = 1.9 Hz), 129.6 (d, J = 2.0 Hz), 129.1 (s), 128.7 (s), 128.0 (dd, J = 17.1, 8.3 Hz), 127.6 (d, J = 19.0 Hz), 127.2 (d, J = 3.0 Hz), 126.6− 126.1 (m), 120.7 (s), 119.9 (s), 110.3 (s), 107.9 (s), 53.9 (s), 53.2 (s), 52.8 (d, J = 16.8 Hz), 51.8 (d, J = 17.1 Hz). IR (KBr): νmax (cm−1) = 3005, 2919, 2848, 2349, 1767, 1746, 1447, 1336, 1275, 1160, 763, 750, 585. HRMS (ESI-TOF): calcd for C22H19FNaO4S [M + Na]+ 421.0887, found 421.0880. 2-((1R,2R)-1-Fluoro-1-nitro-1-(phenylsulfonyl)but-3-en-2-yl)naphthalene (3h). Colorless oil; 86% yield (66.2 mg); 96% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/ 10; flow rate = 0.5 mL/min; detection wavelength = 214 nm; tR = 29.06 (minor), 30.11 (major), 34.19 (major), 39.90 (minor) min]. [α]D20 = −46.8 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.95 (d, J = 7.9 Hz, 2H), 7.84−7.64 (m, 16H), 7.58 (d, J = 8.0 Hz, 2H), 7.49 (t, J = 9.7 Hz, 7H), 7.32 (dd, J = 26.1, 6.3 Hz, 11H), 6.98 (t, J = 7.8 Hz, 5H), 6.36−6.24 (m, 1H), 6.01 (dt, J = 16.9, 9.7 Hz, 3H), 5.48 (dd, J = 26.3, 13.5 Hz, 2H), 5.30 (dd, J = 27.4, 13.4 Hz, 5H), 5.22− 5.11 (m, 1H), 5.05 (dd, J = 31.4, 9.2 Hz, 3H). 19F NMR (377 MHz, CDCl3): δ −127.09 (s), −129.93 (s). 13C NMR (101 MHz, CDCl3): δ 139.1 (s), 136.3 (d, J = 18.5 Hz), 135.1 (s), 133.6−132.9 (m), 132.9 (s), 132.4 (s), 131.3 (s), 131.0 (d, J = 13.7 Hz), 130.8−130.2 (m), 130.0−129.6 (m), 129.5 (s), 129.1 (s), 128.7 (d, J = 6.8 Hz), 128.4 (s), 128.1 (d, J = 4.3 Hz), 127.6 (d, J = 11.2 Hz), 127.2 (s), 127.0− 126.3 (m), 126.1 (s), 125.8 (d, J = 2.0 Hz), 124.3 (s), 123.3 (s), 122.6 (s), 122.2 (s), 53.3 (d, J = 15.4 Hz), 52.4 (d, J = 15.7 Hz). IR (KBr): νmax (cm−1) = 3065, 2359, 2341, 1733, 1577, 1512, 1352, 1159, 1158, 751, 684, 584. HRMS (ESI-TOF): calcd for C20H16FNNaO4S [M + Na]+ 408.0680, found 408.0676. Ethyl (2R,3R)-2-Fluoro-2-(naphthalen-2-ylsulfonyl)-3-phenylpent-4-enoate (3i). Colorless oil; 93% yield (76.6 mg); 87% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/10; flow rate = 0.5 mL/min; detection wavelength = 214 nm; tR = 44.96 (minor), 47.36 (major), 54.58 (major), 59.44 (minor) min]. [α]D20 = −105.5 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 8.51 (s, 3H), 8.03−7.81 (m, 14H), 7.77−7.49 (m, 11H), 7.27 (s, 4H), 7.24 (s, 4H), 7.09 (d, J = 3.1 Hz, 3H), 6.33−6.17 (m, 3H), 6.02 (dt, J = 17.0, 9.7 Hz, 1H), 5.33 (dd, J = 31.8, 13.7 Hz, 6H), 5.28−5.16 (m, 2H), 4.73 (dd, J = 32.8, 8.7 Hz, 3H), 4.60 (dd, J = 33.0, 9.3 Hz, 1H),

4.36−4.24 (m, 2H), 3.79−3.63 (m, 6H), 1.30 (t, J = 7.1 Hz, 3H), 0.80 (t, J = 7.1 Hz, 9H). 19F NMR (377 MHz, CDCl3): δ −161.79 (s), −163.70 (s). 13C NMR (101 MHz, CDCl3): δ 163.6 (s), 163.3 (d, J = 6.6 Hz), 163.0 (s), 136.9 (s), 135.8 (s), 135.4 (s), 134.9 (s), 133.7 (d, J = 3.6 Hz), 133.0 (s), 132.6 (dd, J = 13.5, 9.7 Hz), 131.8 (d, J = 19.2 Hz), 129.9 (dd, J = 25.5, 10.2 Hz), 128.9 (dd, J = 12.4, 10.3 Hz), 128.5 (s), 128.3−127.7 (m), 127.2 (s), 124.5 (s), 124.2 (s), 120.3 (s), 119.7 (s), 110.8 (s), 110.2 (s), 108.4 (s), 107.8 (s), 63.5 (s), 62.9 (s), 52.7 (d, J = 17.0 Hz), 51.9 (d, J = 17.1 Hz), 14.0 (s), 13.4 (s). IR (KBr): νmax (cm−1) = 3005, 2918, 2348, 1769, 1645, 1446, 1333, 1278, 764, 746, 598. HRMS (ESI-TOF): calcd for C23H21FNaO4S [M + Na]+ 435.1041, found 435.1037. Ethyl (2R,3R)-2-Fluoro-2-((3-methoxyphenyl)sulfonyl)-3-phenylpent-4-enoate (3j). Colorless oil; 81% yield (63.5 mg); 95% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/10; flow rate = 0.5 mL/min; detection wavelength = 214 nm; tR = 24.37 (major), 28.61 (minor), 33.53 (minor), 41.51 (major) min]. [α]D20 = −133.1 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.51 (d, J = 7.6 Hz, 3H), 7.47−7.38 (m, 7H), 7.20 (d, J = 7.5 Hz, 8H), 7.04 (dd, J = 22.2, 12.4 Hz, 3H), 6.28 (ddd, J = 17.2, 9.9, 8.9 Hz, 3H), 6.04 (dt, J = 17.0, 9.7 Hz, 1H), 5.32 (t, J = 14.1 Hz, 7H), 5.22 (dd, J = 22.8, 13.4 Hz, 2H), 4.69 (dd, J = 32.7, 8.6 Hz, 3H), 4.55 (dd, J = 32.5, 9.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 2H), 3.85 (s, 10H), 3.76 (dd, J = 8.4, 5.9 Hz, 8H), 1.30 (t, J = 7.1 Hz, 3H), 0.87 (t, J = 7.1 Hz, 10H). 19F NMR (377 MHz, CDCl3): δ −161.85 (s), −163.84 (s). 13C NMR (101 MHz, CDCl3): δ 163.5 (s), 163.2 (d, J = 2.3 Hz), 163.0 (s), 159.8 (s), 159.4 (s), 136.7 (t, J = 14.7 Hz), 135.1 (s), 133.7 (d, J = 3.8 Hz), 132.6 (d, J = 5.4 Hz), 129.9 (s), 129.5 (s), 129.1−128.7 (m), 128.5 (d, J = 4.5 Hz), 128.0 (s), 127.3 (s), 122.6 (s), 122.4 (s), 121.7 (s), 121.2 (s), 120.3 (s), 119.7 (s), 114.5 (s), 114.0 (s), 110.0 (s), 108.23 (s), 107.5 (s), 63.5 (s), 62.9 (s), 55.7 (d, J = 15.5 Hz), 52.5 (d, J = 17.0 Hz), 51.8 (d, J = 17.2 Hz), 14.0 (s), 13.5 (s). IR (KBr): νmax (cm−1) = 3070, 2950, 2348, 1768, 1746, 1448, 1337, 1252, 1160, 1136, 1083, 715, 687, 601. HRMS (ESI-TOF): calcd for C20H21FNaO5S [M + Na]+ 415.0992, found 415.0986. Methyl (2R,3S)-2-Fluoro-3-methyl-2-(phenylsulfonyl)pent-4enoate (3k). Colorless oil; 70% yield (40.0 mg); 96% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/ 10; flow rate = 0.8 mL/min; detection wavelength = 214 nm; tR = 27.08 (minor), 35.40 (major), 37.79 (major), 50.48 (minor) min]. [α]D20 = −48.5 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.90 (dd, J = 7.3, 5.1 Hz, 4H), 7.70 (t, J = 7.4 Hz, 2H), 7.57 (dt, J = 9.9, 5.0 Hz, 4H), 5.86 (ddd, J = 17.4, 10.1, 8.6 Hz, 1H), 5.73 (dt, J = 17.2, 9.6 Hz, 1H), 5.28 (dd, J = 37.2, 14.1 Hz, 2H), 5.17 (dd, J = 23.1, 14.0 Hz, 2H), 3.65 (s, 3H), 3.52 (s, 3H), 1.40 (d, J = 6.9 Hz, 3H), 1.17 (d, J = 7.1 Hz, 3H). 19F NMR (377 MHz, CDCl3): δ −164.45 (s), −166.92 (s). 13C NMR (101 MHz, CDCl3): δ 164.5 (s), 164.2 (s), 135.8 (s), 135.6 (s), 135.2 (d, J = 2.4 Hz), 134.9 (d, J = 6.2 Hz), 134.0 (d, J = 3.1 Hz), 130.4 (s), 129.9 (s), 129.1 (d, J = 15.6 Hz), 119.0 (s), 118.8 (s), 110.0 (d, J = 12.1 Hz), 107.6 (d, J = 13.8 Hz), 77.4 (s), 77.1 (s), 76.8 (s), 53.4 (s), 53.2 (s), 41.2 (d, J = 19.2 Hz), 40.8 (d, J = 18.9 Hz), 15.9 (d, J = 3.6 Hz), 14.3 (d, J = 4.0 Hz). IR (KBr): νmax (cm−1) = 3005, 2956, 2921, 2849, 2360, 2341, 1762, 1748, 1644, 1335, 1275, 1260, 1159, 763, 749. HRMS (ESI+): calcd for C13H15FNaO4S [M + Na]+ 309.0556, found 309.0567. General Procedure for the Synthesis of 5a. In a 50 mL flamedried round-bottomed flask, DIBAL-H (1.27 mL, 1.0 M in toluene, 1.27 mmol) was added slowly to a solution of 3c (180.0 mg, 0.42 mmol) in toluene (10 mL) at −78 °C. The mixture was stirred for 2 h at −78 °C and then quenched with NH4Cl (aq), and organic materials were extracted with ethyl acetate (20 mL × 3). The combined extracts were washed with brine and dried over anhydrous Na2SO4. The solvent was concentrated under reduced pressure by an aspirator, and the residue was purified by the column chromatography (SiO2) with petroleum ether and ethyl acetate (5/1) as eluent to give the aldehyde 5a. (2R,3R)-3-(4-Bromophenyl)-2-fluoro-2-(phenylsulfonyl)pent-4enal (5a). Pale yellow oil; 85% yield (145.0 mg); 98% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 90/ 10; flow rate = 0.5 mL/min; detection wavelength = 214 nm; tR = 10697

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698

Note

The Journal of Organic Chemistry 37.16 (major), 39.39 (minor) min]. [α]D20 = −76.18 (c 1.0, CH3OH). 1 H NMR (400 MHz, CDCl3): δ 9.18 (d, J = 8.1 Hz, 1H), 7.85 (d, J = 8.0 Hz, 2H), 7.71 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.8 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 7.7 Hz, 2H), 6.31 (ddd, J = 17.9, 10.1, 8.2 Hz, 1H), 5.28 (dd, J = 29.6, 13.6 Hz, 2H), 4.70 (dd, J = 31.7, 8.1 Hz, 1H). 19F NMR (376 MHz, CDCl3): δ −171.84 (s). 13C NMR (101 MHz, CDCl3): δ 190.5 (s), 190.2 (s), 135.5 (s), 135.2 (s), 134.4 (s), 132.4 (s), 131.9 (d, J = 5.0 Hz), 131.0 (d, J = 2.0 Hz), 130.3 (s), 129.5 (s), 122.6 (s), 120.8 (s), 110.1 (s), 107.7 (s), 49.6 (d, J = 17.5 Hz). IR (KBr): νmax (cm−1) = 2924, 2348, 1912, 1737, 1690, 1548, 1486, 1331, 1275, 1260, 1149, 764, 750. HRMS (ESI-TOF): calcd for C17H14BrFNaO3S [M + Na]+ 418.9718, found 418.9723. General Procedure for the Synthesis of 7a. In a Schlenk tube were placed NH2OH·HCl (13.8 mg, 0.20 mmol) and the aldehyde 5a (39.6 mg, 0.10 mmol), DCM (1.0 mL) was added, and then triethylamine (TEA, 43 μL, 0.30 mmol) was added. The mixture was magnetically stirred at 25 °C for 3 h. After the completion of the reaction, it was quenched with water and extracted with DCM. The combined extracts were dried over anhydrous Na2SO4. The solvent was concentrated under reduced pressure by an aspirator, and the residue was purified with preparative TLC (PE/EA = 5/1) to give the compound 7a. (2S,3S,4S)-3-(4-Bromophenyl)-4-fluoro-2-methyl-4-(phenylsulfonyl)-3,4-dihydro-2H-pyrrole 1-Oxide (7a). Pale yellow oil; 80% yield (33.2 mg), dr >20/1; 97% ee [Daicel CHIRALCEL AD-H (0.46 cm × 25 cm); n-hexane/2-propanol = 95/5; flow rate = 0.5 mL/min; detection wavelength = 214 nm; tR = 7.72 (major), 7.96 (minor) min]. [α]D20 = −47.64 (c 1.0, CH3OH). 1H NMR (400 MHz, CDCl3): δ 7.63 (t, J = 6.6 Hz, 1H), 7.49 (d, J = 6.9 Hz, 2H), 7.40 (dd, J = 18.9, 7.7 Hz, 4H), 7.13 (d, J = 7.6 Hz, 2H), 6.84 (s, 1H), 4.94 (d, J = 6.6 Hz, 1H), 3.82 (dd, J = 22.6, 9.7 Hz, 1H), 1.53 (d, J = 6.1 Hz, 3H). 19F NMR (377 MHz, CDCl3): δ −138.65 (s). 13C NMR (101 MHz, CDCl3): δ 135.5 (s), 134.5 (s), 132.0 (s), 131.1 (s), 129.4 (s), 129.1 (s), 128.3 (s), 125.5 (d, J = 26.8 Hz), 123.4 (s), 110.3 (d, J = 231.9 Hz), 71.2 (d, J = 2.4 Hz), 56.8 (d, J = 17.4 Hz), 15.6 (s). IR (KBr): νmax (cm−1) = 2956, 2921, 2851, 2359, 2342, 1683, 1558, 1560, 1313, 1275, 1260, 1150, 764, 750. HRMS (ESI-TOF): calcd for C17H15BrFNNaO3S [M + Na]+ 433.9821, found 433.9832.

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Hamashima, Y.; Sodeoka, M. Adv. Synth. Catal. 2010, 352, 2708−2732. (c) Liang, T.; Neumann, C. N.; Ritter, T. Angew. Chem., Int. Ed. 2013, 52, 8214−8264. (d) Bégué, J. P.; Bonnet-Delpon, D. Bioorganic and Medicinal Chemistry of Fluorine; Wiley, 2008. (e) Kirsch, P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, 2nd ed.; Wiley-VCH: Weinheim, 2013. (2) (a) Chu, C. K.; Cheng, Y. C.; Pai, B. S.; Yao, G. Q. U.S. Patent 5,587,362, 1996. (b) Marcellin, P.; Mommeja-Marin, H.; Sacks, S. L.; Lau, G. K.; Sereni, D.; Bronowicki, J. P.; Mondou, E. Hepatology 2004, 40, 140−148. (c) Montgomery, J. A.; Shortnacy-Fowler, A. T.; Clayton, S. D.; Riordan, J. M.; Secrist, J. A. J., III J. Med. Chem. 1992, 35, 397−401. (d) Sorbera, L. A.; Serradell, N.; Bolos, J. Drugs Future 2007, 32, 12−16. (e) Yamaguchi, M.; Yasueda, S. I.; Isowaki, A.; Yamamoto, M.; Kimura, M.; Inada, K.; Ohtori, A. Int. J. Pharm. 2005, 301, 121−128. (3) For selected examples, see: (a) Fukuzumi, T.; Shibata, N.; Sugiura, M.; Yasui, H.; Nakamura, S.; Toru, T. Angew. Chem., Int. Ed. 2006, 45, 4973−4977. (b) Bélanger, E.; Cantin, K.; Messe, O.; Tremblay, M.; Paquin, J. F. J. Am. Chem. Soc. 2007, 129, 1034−1035. (c) Liu, W. B.; Zheng, S. C.; He, H.; Zhao, X. M.; Dai, L. X.; You, S. L. Chem. Commun. 2009, 6604−6606. (4) FBSM was respectively reported by Shibata and Hu in 2006; see ref 6a and: (a) Ni, C.; Li, Y.; Hu, J. J. Org. Chem. 2006, 71, 6829−6833. (b) Yang, W.; Wei, X.; Pan, Y.; Lee, R.; Zhu, B.; Liu, H.; Yan, L.; Huang, K.; Jiang, Z.; Tan, C. Chem. - Eur. J. 2011, 17, 8066−8087. (5) (a) Buchanan, R. L.; Pattison, F. L. M. Can. J. Chem. 1965, 43, 3466. (b) Harsanyi, A.; Sandford, G. Org. Process Res. Dev. 2014, 18, 981−992. (6) Pd-catalyzed asymmetrical allylations of 2-fluoromalonate, FBSM, and ethyl 2-fluoro-2-(diethoxyphosphoryl)acetate were respectively described; see: (a) Kawasaki, T.; Kitazume, T. Isr. J. Chem. 1999, 39, 129−131. (b) Jiang, B.; Huang, Z. G.; Cheng, K. J. Tetrahedron: Asymmetry 2006, 17, 942−951. (c) Shibatomi, K.; Muto, T.; Sumikawa, Y.; Narayama, A.; Iwasa, S. Synlett 2009, 2009, 241−244. (d) Zhao, X.; Liu, D.; Zheng, S.; Gao, N. Tetrahedron Lett. 2011, 52, 665−667. (e) Huang, Y.; Zhang, Q.-S.; Fang, P.; Chen, T. G.; Zhu, J.; Hou, X. L. Chem. Commun. 2014, 50, 6751−6753. (f) Su, H.; Xie, Y.; Liu, W.; You, S. Bioorg. Med. Chem. Lett. 2011, 21, 3578−3582. (7) Selected reviews: (a) Hartwig, J. F.; Stanley, L. M. Acc. Chem. Res. 2010, 43, 1461−1475. (b) Hartwig, J. F.; Pouy, M. J. Top. Organomet. Chem. 2011, 34, 169−208. (c) Liu, W. B.; Xia, J. B.; You, S. L. Top. Organomet. Chem. 2011, 38, 155−208. Selected papers: (d) Kiener, C. A.; Shu, C.; Incarvito, C.; Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 14272−14273. (e) Qu, J.; Roßberg, L.; Helmchen, G. J. Am. Chem. Soc. 2014, 136, 1272−1275. (f) Liu, W.-B.; Okamoto, N.; Alexy, E. J.; Hong, A. Y.; Tran, K.; Stoltz, B. M. J. Am. Chem. Soc. 2016, 138, 5234−5237. (8) Ir-catalyzed allylation was reported; see: (a) Liu, W. B.; Reeves, C. M.; Stoltz, B. M. J. Am. Chem. Soc. 2013, 135, 17298−17301. (b) Zhang, H. B.; Chen, J. T.; Zhao, X. M. Org. Biomol. Chem. 2016, 14, 7183−7186. (9) (a) Goehler, S.; Stark, C. B. W. Org. Biomol. Chem. 2007, 5, 1605−1614. (b) Laurenson, J. A. B.; Percy, J. M.; Meiries, S.; Roig, R. Tetrahedron Lett. 2009, 50, 3571−3573. (c) Li, Q.; Wang, W.; Berst, K. B.; Laiborne, A.; Hasvold, L. Bioorg. Med. Chem. Lett. 1998, 8, 1953− 1958. (d) Shibatomi, K.; Kobayashi, F.; Narayama, A.; Fujisawa, I.; Iwasa, S. Chem. Commun. 2012, 48, 413−415. (e) Cox, J. M.; Hawkes, T. R.; Bellini, P.; Ellis, R. M.; Barrett, R. Pestic. Sci. 1997, 50, 297−311. (10) CCDC-1555748, 3c, contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif. (11) Siddiqui, S. M.; Azam, A. Med. Chem. Res. 2014, 23, 2976−2984. (12) CCDC-1561709, 7a, contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b01782. 1 H, 13C, and 19F NMR spectra for all isolated products (PDF) X-ray data of compound 3c (CIF) X-ray data of compound 7a (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Xiaoming Zhao: 0000-0002-1447-128X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful to the Chinese National Science Foundation (NSF) (Grant No. 21272175) and the Shanghai Science and Technology Commission (14DZ2261100) for financial support of this research.

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REFERENCES

(1) (1) For selected papers or reviews or books, see: (a) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470−477. (b) Lectard, S.; 10698

DOI: 10.1021/acs.joc.7b01782 J. Org. Chem. 2017, 82, 10693−10698