Note Cite This: J. Org. Chem. 2018, 83, 9449−9455
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Copper-Catalyzed Oxidative Trifunctionalization of Olefins: An Access to Functionalized β‑Keto Thiosulfones Shuai Huang,† Nuligonda Thirupathi,† Chen-Ho Tung,† and Zhenghu Xu*,†,‡ †
J. Org. Chem. 2018.83:9449-9455. Downloaded from pubs.acs.org by EASTERN KENTUCKY UNIV on 08/17/18. For personal use only.
Key Lab of Colloid and Interface Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, no. 27 South Shanda Road, Jinan, Shandong 250100, China ‡ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. China S Supporting Information *
ABSTRACT: Aerobic oxidative trifunctionalization of olefins for the synthesis of functionalized β-keto thiosulfones has been described. The transformation proceeds through molecular oxygen activation under copper catalysis and forms the two new C−S bonds in a single operation using mild conditions. A novel Cu-catalyzed sulfonyl radical addition/oxidation/funtionalization relay mechanism was proposed for the discovered reaction.
I
Scheme 1. Oxidative Alkene Functionalization Reactions
n past few decades, oxidative difunctionalization of olefins has attracted great attention,1 as it introduces diverse functional groups through the formation of a carbonyl group and another new C−C or C−heteroatom bond.2 Consequently, numerous synthetic efforts have been made in this direction toward the great success. Although significant progress has been made toward the oxidative difunctionalization of olefins, reactions toward the trifunctionalization of olefins,3 where the synergistic formation of a carbonyl group and two new C−C or C−X bonds has not been explored. The major reason may be due to the lack of an effective method to realize such challenging transformations. On the other hand, organo sulfur compounds are ubiquitously found in a large number of natural products and chiral ligands and have gained a sizable attention due to the wide range of biological and medicinal properties.4 Among them, substituted β-thiofunctionalized ketones particularly occupy a pivotal position, since they are not only found in the structures of bioactive and drug molecules but also important building blocks in organic synthesis.5 In this context, numerous synthetic methods toward thiofunctionalize ketones have been developed (Scheme 1).6 Typically β-thiofunctionalized ketones are synthesized from the nucleophilic substitution on α-halo carbonyl compounds in the presence of thiolates.7 Recently, Zhang reported a [2,3]-sigmatropic rearrangement reaction between allyl sulfide and in situ generated carbene intermediate.6b The Lei group reported an oxygen promoted oxidatve difunctionalizaton reaction to βketo sulfides and sulfones from vinylphosphates under catalystfree conditions.6c Although useful, many of the reported methods suffer from severe drawbacks such as harsh reaction conditions, longer reaction times, limited substrate scope, low yields, and the prefunctionalization of starting materials.8 All of the above approaches can only introduce one sulfur atom adjacent to carbonyl group. Therefore, the development of new © 2018 American Chemical Society
and efficient synthetic methods, particularly that starting from readily available starting materials, to construct a diverse functionalized β-thio ketone is highly desirable. Herein, we report the first copper-catalyzed alkene oxidative trifunctionalization reaction, which synergistically forms one carbonyl group and two new C−S bonds under mild conditions. Previously, we developed a gold/photoredox-mediated alkene disulfuration reaction by using electrophilic S-phenyl benzenesulfonothioate.9 Inspired by recent reports on alkene oxidative functionalization,10 we became curious about the oxidative functionalization of styrene with benzenesulfonothioate. Initially we choose styrene 1a and S-butyl benzenesulfonothioate 2a as model substrates. Pleasingly, the trifunctionalized product 3a was isolated in 46% yields in the presence of 20 mol % of copper(I)-thiophene-2-carboxylate, Received: May 7, 2018 Published: July 20, 2018 9449
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
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The Journal of Organic Chemistry
atmosphere, only traces of the product were observed (entry 13). After having the optimal conditions in hand, we next investigated the scope and limitation of the method. First, a variety of commercially available styrene derivatives (1a−o) were exposed to standard reaction conditions, and the results are presented in Table 2. A variety of electronically rich,
together with 20 mol % of bipyridine (bpy) ligand in MeCN at 80 °C under air (Scheme 2). Further, the structure of product 3a was unambiguously characterized by single X-ray analysis. Scheme 2. Initial Formation of the Trifunctionalization Product
Table 2. Substrate Scope of Alkenes for the Synthesis of βKeto Thioethersa
Encouraged by this initial result, we next focused our attention toward the optimization of the reaction conditions (Table 1). Various solvents were tested first (entries 1−4), the reaction proceeded also very well in other polar solvents such as DMF and DMSO, and the latter was found as the best solvent, giving the target product in 62% yield (entry 4). Toluene could not deliver any product. Performing the reaction in CH3CN also produced the desired product in reasonable yield (entry 1). These data indicated that the oxygen atom in the final product came from molecular oxygen, but not from the solvent DMSO. Other commonly used copper catalysts such as Cu(OTf)2 and Cu(CH3CN)4PF6 were also screened and found to be less productive. Other oxidants such as H2O2 and 1,4-benzoquinone under the same conditions provided diminished yields (entries 8 and 9). Lowering the temperature to 50 °C and adding 10 equiv of water slightly improved the reaction yield to 68% yield (entry 11). Finally, the product could be isolated in the highest 75% yield by increasing the loading of the thiolation reagent 2a (entry 12). When performing the reaction under nitrogen
a
Reaction conditions: 1a (0.2 mmol), 2 (0.6 mmol), copper thiophene-2-carboxylate (20 mol %), bpy (20 mol %), DMSO (1 mL), H2O (36 mg), 50 °C, 12 h, in the air. bLigand: 1,10-phen instead of bpy; reaction time: 24 h; 80 °C.
neutral, and poor styrenes were well tolerated under the standard conditions and afforded the corresponding αfunctionalized β-keto thioethers (3a−q) in moderate to good yields (28−75%). Various functional groups at the para
Table 1. Optimization of Reaction Conditionsa
entry
catalyst
ligand
temp (°C)
solvent
additiveb
yield(%)c
1 2 3 4 5 6 7 8 9 10 11 12 13
CuTC CuTC CuTC CuTC CuTC Cu(OTf)2 Cu(MeCN)4PF6 CuTC CuTC CuTC CuTC CuTC CuTC
bpy bpy bpy bpy 1,10-phen 1,10-phen 1,10-phen bpy bpy bpy bpy bpy bpy
80 80 80 80 80 80 80 80 80 50 50 50 50
MeCN DMF toluene DMSO DMSO DMSO DMSO MeCN MeCN DMSO DMSO DMSO DMSO
− − − − − − − H2O2 quinone − H2O H2O H2O
46 45 0 62 55 trace 48 42 0 64 68 75d tracee
a
Reaction conditions: Styrene 1a (0.2 mmol), PhSO2SC4H9 2a (0.4 mmol), catalyst (20 mmol %), bpy (20 mmol %) in solvent (1 mL), in the air. H2O2 (0.4 mmol), or quinone (1,4-benzoquinone, 0.4 mmol), or H2O (2 mmol). cIsolated yield. dPhSO2SC4H9 (0.6 mmol). eUnder N2 atmosphere. b
9450
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
Note
The Journal of Organic Chemistry position of styrene such as alkyl, fluoro, chloro, bromo, cyano, methoxy, and acetoxy were well tolerated and produced the corresponding β-keto thioethers (3a−i) in moderate to good yields (45−75%). Methylstyrene 1o and indene 1p also afforded the corresponding ketones (3o, and 3p), albeit in low yields (38 and 43%). Vinylnaphthalene 1o also produced corresponding β-keto thioether (3q) without much complication. However, aliphatic alkenes are not suitable for this transformation under this conditions. Then we turned to investigate the scope of the oxidative trifunctionalization reaction with respective to PhSO2SR. Thus, a variety of S-alkyl benzenesulfonothioates were reacted with styrene under the optimized conditions, and results are summarized in Table 3. A variety of S-alkyl benzenesulfono-
Scheme 3. Control Experiments
Table 3. Substrate Scope of PhSO2SR for the Synthesis of βKeto Thioethersa step is a fast reaction, and indeed the reaction of 5 with 2a could produce sulfenylation product 3a in 92% yield in the presence of base without copper catalyst under N2 atmosphere (eq 4, Scheme 3). Based on these results and literature precedents, a possible reaction mechanism has been proposed as depicted in Scheme 4. First, S-phenyl benzenesulfonothioate 1 may react with Scheme 4. Possible Reaction Pathways
a
Reaction conditions: 1a (0.2 mmol), 2 (0.6 mmol), copper thiophene-2-carboxylate (20 mol %), bpy (20 mol %), DMSO (1 mL), H2O (36 mg), 50 °C, 12 h in the air. bLigand: 1,10-phen instead of bpy; reaction time: 24 h; 80 °C.
thioates 2 were synthesized. As it is evident in Table 3, S-alkyl benzenesulfonothioates (2b−i) were tolerated to standard conditions and afforded corresponding β-keto thioether derivatives (3r−y) in good yields (50−70%). S-Aryl benzenesulfonothioates (2j and 2k) also produced corresponding β-keto sulfides (3z and 3aa) with moderate yields. Unfortunately, Se-phenyl benzenesulfonothioate substrate 2l is less reactive in standard conditions and produced the corresponding β-keto sulfides 3ab in lower (37%) yield. Several control experiments were conducted to explore the mechanism of this reaction. When radical scavenger was added in the reaction system, no product was formed (eq 1, Scheme 3). Since styrenes can be aerobically oxidized to aldehyde and acetophenone, the reaction of acetophenone 4 under standard reaction was performed and did not lead to any products (eq 2, Scheme 3), which indicated that acetophenone is not a reaction intermediate. The reaction of β-keto sulfone 5 with 2a under standard conditions gave product 3a in 58% yield (eq 3, Scheme 3), indicating 5 might be a possible reaction intermediate. However, we could not detect or isolate 5 from the reaction mixture, a possible reason might be that this
copper(I) catalyst to produce sulfonyl radical, which could react with styrene to produce radical intermediate A. Intermediate A produces the peroxy radical B by activating molecular oxygen in the presence of L-[Cu]SC4H 9. 1i Fragmentation of peroxy radical produces the β-keto sulfone C, which would then react with the expelled L-[CuOH]+1h to produce intermediate D. Finally, intermediate D yields the title product via reductive elimination and regenerates the copper catalyst. In summary, the first copper-catalyzed trifunctionalization of alkenes via O2 activation has been developed. The attractive features of the method include commercial accessibility and stability of starting materials, experimental simplicity, broad substrate scope, and mild reaction conditions, providing an easy and reliable access to β-thiofunctionalize ketones in good yields. This strategy can be applied in other oxidative alkene trifunctionalization reactions. 9451
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
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The Journal of Organic Chemistry
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(m, 2H), 1.35−1.31 (m, 2H), 0.85 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 187.6, 167.4, 165.4, 136.2, 134.4, 132.0, 131.9, 130.5, 128.7, 116.2, 116.1, 71.1, 32.5, 30.8, 21.7, 13.5. HRMS (ESITOF) m/z: [M + Na]+ calcd for C18H19O3S2FNa 389.0652; found 389.0655. 2-(Butylthio)-1-(4-chlorophenyl)-2-(phenylsulfonyl)ethan-1-one (3e). White solid (45.7 mg, 60%). 1H NMR (500 MHz, CDCl3) δ 7.98 (dd, J = 8.4, 1.2 Hz, 2H), 7.94−7.90 (m, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.46 (d, J = 8.6 Hz, 2H), 5.51 (s, 1H), 2.90−2.69 (m, 2H), 1.54−1.46 (m, 2H), 1.37−1.29 (m, 2H), 0.86 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.0, 141.0, 136.1, 134.5, 133.3, 130.5, 130.5, 129.3, 128.7, 71.0, 32.5, 30.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C18H23O3S2ClN 400.0802; found 400.0803. 1-(4-Bromophenyl)-2-(butylthio)-2-(phenylsulfonyl)ethan-1-one (3f). White solid (56.3 mg, 66%). 1H NMR (500 MHz, CDCl3) δ 7.98 (dd, J = 8.3, 1.0 Hz, 2H), 7.84 (d, J = 8.6 Hz, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.62 (d, J = 8.6 Hz, 2H), 7.56 (t, J = 7.8 Hz, 2H), 5.51 (s, 1H), 2.90−2.68 (m, 2H), 1.56−1.44 (m, 2H), 1.36−1.30 (m, 2H), 0.86 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.2, 136.1, 134.5, 133.7, 132.3, 130.6, 129.9, 128.7, 71.0, 32.5, 30.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C18H23O3S2BrN 444.0297; found 444.0286. 4-(2-(Butylthio)-2-(phenylsulfonyl)acetyl)benzonitrile (3g). White solid (33.9 mg, 45%). 1H NMR (500 MHz, CDCl3) δ 8.08 (d, J = 8.5 Hz, 2H), 7.98 (dd, J = 8.4, 1.2 Hz, 2H), 7.79 (d, J = 8.6 Hz, 2H), 7.71 (t, J = 7.5 Hz, 1H), 7.58 (t, J = 7.8 Hz, 2H), 5.52 (s, 1H), 2.88−2.69 (m, 2H), 1.52−1.47 (m, 2H), 1.35−1.30 (m, 2H), 0.86 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.0, 138.0, 136.0, 134.7, 132.7, 130.5, 129.5, 128.8, 117.6, 117.4, 71.2, 32.6, 30.8, 21.7, 13.5. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C19H19NO3S2Na 396.0699; found 396.0695. 2-(Butylthio)-1-(4-methoxyphenyl)-2-(phenylsulfonyl)ethan-1one (3h). White solid (54.9 mg, 73%). 1H NMR (500 MHz, CDCl3) δ 7.97 (dd, J = 17.6, 8.2 Hz, 4H), 7.66 (t, J = 7.5 Hz, 1H), 7.54 (t, J = 7.8 Hz, 2H), 6.94 (d, J = 8.9 Hz, 2H), 5.54 (s, 1H), 3.87 (s, 3H), 2.89−2.70 (m, 2H), 1.57−1.45 (m, 2H), 1.36−1.31 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 187.4, 164.6, 136.4, 134.3, 131.6, 130.6, 128.6, 127.9, 114.14, 71.0, 55.7, 32.5, 30.9, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C19H22O4S2Na 401.0852; found 401.0846. 4-(2-(Butylthio)-2-(phenylsulfonyl)acetyl)phenyl acetate (3i). White solid (55.2 mg, 61%). 1H NMR (500 MHz, CDCl3) δ 8.00 (t, J = 7.6 Hz, 4H), 7.67 (t, J = 7.5 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.22 (d, J = 8.8 Hz, 2H), 5.56 (d, J = 1.8 Hz, 1H), 2.91−2.68 (m, 2H), 2.32 (s, 3H), 1.56−1.45 (m, 2H), 1.36−1.29 (m, 2H), 0.85 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 187.9, 168.7, 155.3, 136.3, 134.4, 132.5, 130.8, 130.5, 128.7, 122.1, 70.8, 32.4, 30.8, 21.8, 21.2, 13.8, 13.6. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C20H26O5S2N 424.1247; found 424.1253. 2-(Butylthio)-2-(phenylsulfonyl)-1-(o-tolyl)ethan-1-one (3j). White solid (40.3 mg, 56%). 1H NMR (500 MHz, CDCl3) δ 8.03− 7.98 (m, 2H), 7.74 (d, J = 7.7 Hz, 1H), 7.68 (t, J = 7.5 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.41 (t, J = 7.5 Hz, 1H), 7.26 (t, J = 7.3 Hz, 2H), 5.39 (s, 1H), 2.96−2.75 (m, 2H), 2.42 (s, 3H), 1.53 (ddt, J = 21.1, 14.7, 7.6 Hz, 2H), 1.35 (p, J = 7.5 Hz, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 136.5, 134.3, 132.4, 132.1, 130.6, 128.7, 128.6, 125.9, 72.6, 32.7, 30.9, 21.7, 20.9, 13.5. HRMS (ESITOF) m/z: [M + Na]+ calcd for C19H22O3S2Na 385.0903; found 385.0899. 2-(Butylthio)-1-(2-chlorophenyl)-2-(phenylsulfonyl)ethan-1-one (3k). White solid (21.7 mg, 28%). 1H NMR (500 MHz, CDCl3) δ 7.95 (d, J = 7.5 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 3H), 7.36 (dt, J = 14.3, 7.4 Hz, 2H), 7.29 (t, J = 7.4 Hz, 1H), 5.51 (s, 1H), 2.92−2.64 (m, 2H), 1.44 (ddd, J = 21.9, 14.6, 7.6 Hz, 2H), 1.27 (dq, J = 14.2, 7.2 Hz, 2H), 0.80 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 190.5, 134.4, 133.0, 130.7, 130.5, 128.7, 127.2, 73.2, 32.7, 30.8, 21.7, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C18H19O3S2ClNa 405.0356; found 405.0353.
EXPERIMENTAL SECTION
General Details. Unless otherwise noted, all of the reagents were obtained commercially and used without further purification, and reactions were monitored by TLC. Analytic grade solvents for the chromatography were used as received. All NMR spectra were recorded on Bruker-500 MHz spectrometer. HRMS were measured on the Q-TOF6510 instruments. Typical Procedure for the Synthesis of Substituted Benzenesulfonothioate (2a−I). To a solution of PhSO2Na (40 mmol) in n-BuNH2 (40 mL) was added sulfur (42 mmol) at room temperature, and the solution was stirred for 3 h. The reaction mixture was evaporated under reduced pressure to remove the solvent. The residue was washed by Et2O, and a white powder (PhSO2SNa) was obtained. To a solution of PhSO2SNa in EtOH (50 mL) was added n-C4H9I (60 mmol), and then the solution was stirred at 45 °C for 12 h. Upon completion, water (40 mL) was added to the reaction mixture, and the solution was extracted with CH2Cl2 (30 mL × 3). The combined organic layer was dried with anhydrous Na2SO4 and evaporated under reduced pressure. The residue was purified through column chromatography affording the product 2a (silica gel, petroleum ether/ethyl acetate = 30/1). Typical Procedure for Benzenesulfonothioate (2j−k). 2j−k were prepared by a reported procedure.9a Typical Procedure for the Synthesis of Desired Product (3a−z). To a mixture of copper thiophene-2-carboxylate (20 mol %), 2,2′-bipyridine (20 mol %) in solvent (1 mL DMSO + 36 mg water), alkene (0.2 mmol), and thiosulfonylation reagent 2a (0.6 mmol) were added. The reaction system was stirred at 50 °C under air atmosphere for 12 h. Then, the resulting mixture was evaporated under reduced pressure and purified by flash chromatography to afford the desired product 3a (silica gel, petroleum ether/ethyl acetate = 15/1). Procedure for the Synthesis of 1-Phenyl-2(phenylsulfonyl)ethan-1-one (5). To a solution of PhSO2Na (12 mmol) in EtOH (40 mL) was added 2-bromoacetophenone (10 mmol) at room temperature, and the solution was stirred for 12 h. The reaction mixture was evaporated under reduced pressure to remove the solvent. The residue was purified through column chromatography affording the desired product (5). 2-(Butylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1-one (3a). White solid (52.0 mg, 75%): mp 89−91 °C. 1H NMR (500 MHz, CDCl3) δ 8.00 (dd, J = 8.3, 1.1 Hz, 2H), 7.97−7.94 (m, 2H), 7.67 (t, J = 6.9 Hz, 1H), 7.62 (t, J = 6.9 Hz, 1H), 7.55 (t, J = 7.0 Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 5.57 (s, 1H), 2.90−2.71 (m, 2H), 1.51 (m, 2H), 1.33 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.1, 136.3, 135.1, 134.3, 134.3, 130.6, 129.0, 128.9, 128.6, 70.8, 32.5, 30.9, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C18H20O3S2Na 371.0746; found 371.0733. See also Supporting Information. 2-(Butylthio)-2-(phenylsulfonyl)-1-(p-tolyl)ethan-1-one (3b). White solid (51.0 mg, 70%). 1H NMR (500 MHz, CDCl3) δ 7.99 (dd, J = 8.3, 1.1 Hz, 2H), 7.86 (d, J = 8.3 Hz, 2H), 7.66 (t, J = 7.5 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.31−7.25 (m, 2H), 5.57 (s, 1H), 2.90−2.70 (m, 2H), 2.42 (s, 3H), 1.51 (m, 2H), 1.34 (m, 2H), 0.85 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.6, 145.6, 136.3, 134.3, 132.5, 130.6, 129.6, 129.2, 128.6, 70.8, 32.4, 30.9, 21.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na] + calcd for C19H22O3S2Na 385.0903; found 385.0900. 1-(4-(tert-Butyl)phenyl)-2-(butylthio)-2-(phenylsulfonyl)ethan-1one (3c). White solid (61.3 mg, 76%). 1H NMR (500 MHz, CDCl3) δ 8.04−7.97 (m, 2H), 7.91 (d, J = 8.5 Hz, 2H), 7.67 (t, J = 7.5 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 5.58 (s, 1H), 2.91− 2.70 (m, 2H), 1.58−1.45 (m, 2H), 1.38−1.29 (m, 11H), 0.86 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.6, 158.4, 136.3, 134.3, 132.4, 130.6, 129.1, 128.6, 125.9, 70.7, 35.3, 32.5, 31.0, 30.9, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na] + calcd for C22H28O3S2Na 427.1372; found 427.1374. 2-(Butylthio)-1-(4-fluorophenyl)-2-(phenylsulfonyl)ethan-1-one (3d). White solid (45.1 mg, 62%). 1H NMR (500 MHz, CDCl3) δ 8.05−7.96 (m, 4H), 7.68 (t, J = 8.0 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.15 (t, J = 8.6 Hz, 2H), 5.54 (s, 1H), 2.89−2.70 (m, 2H), 1.57−1.44 9452
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
Note
The Journal of Organic Chemistry 2-(Butylthio)-2-(phenylsulfonyl)-1-(m-tolyl)ethan-1-one (3l). White solid (49.2 mg, 68%). 1H NMR (500 MHz, CDCl3) δ 8.03− 7.98 (m, 2H), 7.75 (d, J = 6.8 Hz, 2H), 7.67 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.43 (d, J = 7.5 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 5.58 (s, 1H), 2.92−2.71 (m, 2H), 2.41 (s, 3H), 1.57−1.46 (m, 2H), 1.37−1.31 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.2, 138.9, 136.3, 135.2, 135.1, 134.3, 130.6, 129.4, 128.8, 128.6, 126.2, 70.6, 32.4, 30.9, 21.8, 21.4, 13.6. HRMS (ESI-TOF) m/ z: [M + NH4]+ calcd for C19H26O3S2N 380.1349; found 380.1339. 2-(Butylthio)-1-(3-chlorophenyl)-2-(phenylsulfonyl)ethan-1-one (3m). White solid (43.0 mg, 56%). 1H NMR (500 MHz, CDCl3) δ 8.02−7.96 (m, 2H), 7.91 (t, J = 1.8 Hz, 1H), 7.85 (d, J = 7.9 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.58 (dd, J = 14.8, 7.1 Hz, 3H), 7.44 (t, J = 7.9 Hz, 1H), 5.49 (s, 1H), 2.92−2.70 (m, 2H), 1.58−1.46 (m, 2H), 1.39−1.30 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 188.0, 136.5, 136.1, 135.3, 134.5, 134.2, 130.6, 130.2, 129.0, 128.7, 127.1, 70.9, 32.5, 30.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + H]+ calcd for C18H20O3S2Cl 383.0537; found 383.0525. 1-(3-Bromophenyl)-2-(butylthio)-2-(phenylsulfonyl)ethan-1-one (3n). White solid (55.9 mg, 66%). 1H NMR (500 MHz, CDCl3) δ 8.06 (t, J = 1.7 Hz, 1H), 7.99 (dd, J = 8.3, 1.1 Hz, 2H), 7.90 (d, J = 7.9 Hz, 1H), 7.76−7.72 (m, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.57 (t, J = 7.8 Hz, 2H), 7.37 (t, J = 7.9 Hz, 1H), 5.49 (s, 1H), 2.93−2.69 (m, 2H), 1.55−1.48 (m, 2H), 1.38−1.29 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 187.9, 137.1, 136.7, 136.1, 134.5, 131.9, 130.6, 130.4, 128.7, 127.6, 123.2, 70.8, 32.5, 30.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C18H23O3S2BrN 444.0297; found 444.0294. 2-(Butylthio)-1-phenyl-2-(phenylsulfonyl)propan-1-one (3o). White solid (27.3 mg, 38%). 1H NMR (500 MHz, CDCl3) δ 8.13− 8.04 (m, 4H), 7.65 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.8 Hz, 3H), 7.42 (t, J = 7.8 Hz, 2H), 2.74−2.60 (m, 2H), 1.92 (s, 3H), 1.51−1.44 (m, 2H), 1.33−1.28 (m, 2H), 0.82 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 193.8, 136.6, 136.2, 133.9, 132.9, 131.6, 129.3, 128.4, 128.4, 79.6, 31.7, 30.5, 22.0, 21.4, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C19H22O3S2Na 385.0903; found 385.0899. 2-(Butylthio)-2-(phenylsulfonyl)-2,3-dihydro-1H-inden-1-one (3p). Light gray solid (31.2 mg, 43%). 1H NMR (500 MHz, CDCl3) δ 8.07−8.01 (m, 2H), 7.77 (d, J = 7.7 Hz, 1H), 7.70−7.61 (m, 2H), 7.56 (t, J = 7.8 Hz, 2H), 7.45−7.39 (m, 2H), 4.11 (d, J = 18.0 Hz, 1H), 3.25 (d, J = 18.1 Hz, 1H), 2.90−2.63 (m, 2H), 1.44−1.38 (m, 2H), 1.34−1.27 (m, 2H), 0.84 (t, J = 7.3 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 193.5, 149.5, 136.0, 135.6, 134.4, 134.3, 131.3, 128.5, 128.5, 126.2, 125.5, 75.0, 38.1, 30.8, 30.3, 22.0, 13.6. HRMS (ESITOF) m/z: [M + Na]+ calcd for C19H20O3S2Na 383.0746; found 383.0747. 2-(Butylthio)-1-(naphthalen-2-yl)-2-(phenylsulfonyl)ethan-1-one (3q). White solid (54.8 mg, 69%). 1H NMR (500 MHz, CDCl3) δ 8.52 (s, 1H), 8.05−8.01 (m, 2H), 8.00−7.94 (m, 2H), 7.90−7.69 (m, 2H), 7.68−7.62 (m, 2H), 7.59−7.54 (m, 3H), 5.75 (s, 1H), 2.95− 2.76 (m, 2H), 1.61−1.47 (m, 2H), 1.38−1.32 (m, 2H), 0.85 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.0, 136.3, 136.0, 134.4, 132.3, 131.4, 130.7, 130.0, 129.4, 128.9, 128.7, 127.8, 127.2, 124.0, 71.0, 32.5, 30.9, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C22H22O3S2Na 421.0903; found 421.0908. 2-(Methylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1-one (3r). White solid (40.7 mg, 67%). 1H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 7.9 Hz, 2H), 7.95 (d, J = 7.9 Hz, 2H), 7.68 (t, J = 7.4 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.7 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 5.54 (s, 1H), 2.27 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 188.5, 136.4, 134.9, 134.4, 130.5, 129.0, 128.9, 128.9, 128.8, 70.6, 15.3. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C15H14O3S2Na 329.0277; found 329.0280. 1-Phenyl-2-(phenylsulfonyl)-2-(propylthio)ethan-1-one (3s). White solid (36.5 mg, 55%). 1H NMR (500 MHz, CDCl3) δ 8.06− 7.90 (m, 4H), 7.68 (t, J = 7.5 Hz, 1H), 7.63 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.49 (t, J = 7.8 Hz, 2H), 5.58 (s, 1H), 2.92−2.65 (m, 2H), 1.64−1.50 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.1, 136.2, 135.0, 134.4, 134.4, 130.6, 129.0,
128.9, 128.7, 70.7, 34.7, 22.3, 13.3. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C17H22O3S2N 352.1036; found 352.1042. 2-(Octylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1-one (3t). White solid (43.2 mg, 54%): mp 49−50 °C. 1H NMR (500 MHz, CDCl3) δ 7.98 (dd, J = 22.0, 7.4 Hz, 4H), 7.67 (t, J = 7.5 Hz, 1H), 7.61 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 5.59 (s, 1H), 2.90−2.70 (m, 2H), 1.59−1.44 (m, 2H), 1.32− 1.18 (m, 10H), 0.86 (t, J = 7.1 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.1, 136.3, 135.0, 134.4, 134.3, 130.6, 129.0, 128.9, 128.6, 70.7, 32.8, 31.7, 29.1, 29.0, 28.8, 28.6, 22.6, 14.1. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C22H32O3S2N 422.1818; found 422.1816. 2-(Benzylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1-one (3u). White solid (41.6 mg, 54%). 1H NMR (500 MHz, CDCl3) δ 8.02 (dd, J = 8.3, 1.0 Hz, 2H), 7.67 (t, J = 7.5 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.40−7.33 (m, 7H), 7.26 (dd, J = 11.1, 4.5 Hz, 2H), 5.46 (s, 1H), 4.33 (d, J = 13.0 Hz, 1H), 3.89 (d, J = 13.0 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 189.1, 136.1, 135.8, 134.7, 134.4, 134.2, 130.9, 130.0, 129.1, 128.8, 128.7, 128.5, 128.0, 68.2, 37.1. HRMS (ESI-TOF) m/z: [M + NH4]+ calcd for C21H22O3S2N 400.1036; found 400.1033. 2-(Allylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1-one (3v). White solid (42.3 mg, 64%). 1H NMR (500 MHz, CDCl3) δ 7.98−7.91 (m, 4H), 7.68 (t, J = 7.5 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.55 (dd, J = 8.1, 7.6 Hz, 2H), 7.48 (dd, J = 8.2, 7.5 Hz, 2H), 5.78−5.69 (m, 1H), 5.66 (s, 1H), 5.39−5.30 (m, 2H), 3.73 (dd, J = 13.4, 9.4 Hz, 1H), 3.29 (dd, J = 13.0, 5.4 Hz, 1H). 13C NMR (126 MHz, CDCl3) δ 189.4, 135.9, 135.1, 134.5, 134.4, 132.1, 130.7, 129.2, 128.9, 128.6, 120.6, 68.9, 35.7. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C17H16O3S2Na 355.0433; found 355.0436. (E)-2-(But-2-en-1-ylthio)-1-phenyl-2-(phenylsulfonyl)ethan-1one (3w). White solid (43.3 mg, 60%). 1H NMR (500 MHz, CDCl3) δ 8.01−7.95 (m, 2H), 7.95−7.90 (m, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.48 (t, J = 7.8 Hz, 2H), 5.83−5.76 (m, 1H), 5.65 (s, 1H), 5.41−5.31 (m, 1H), 3.65 (dd, J = 13.2, 9.5 Hz, 1H), 3.26−3.19 (m, 1H), 1.77 (d, J = 6.5 Hz, 3H). 13 C NMR (126 MHz, CDCl3) δ 189.5, 136.1, 135.2, 134.4, 134.3, 132.2, 130.8, 129.1, 128.9, 128.5, 125.1, 68.9, 35.3, 29.7, 17.8. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C18H18O3S2Na 369.0590; found 369.0597. 2-(Butylthio)-1-phenyl-2-tosylethan-1-one (3x). White solid (50.5 mg, 70%). 1H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 7.5 Hz, 2H), 7.86 (d, J = 8.2 Hz, 2H), 7.61 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.8 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 5.56 (s, 1H), 2.92−2.71 (m, 2H), 2.44 (s, 3H), 1.57−1.46 (m, 2H), 1.39−1.29 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.2, 145.5, 135.2, 134.2, 133.3, 130.6, 129.3, 129.0, 128.9, 70.8, 32.5, 30.9, 21.8, 13.5. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C19H22O3S2Na 385.0903; found 385.0907. 2-(Butylthio)-2-((4-chlorophenyl)sulfonyl)-1-phenylethan-1-one (3y). White solid (38.4 mg, 50%). 1H NMR (500 MHz, CDCl3) δ 7.99−7.91 (m, 4H), 7.64 (t, J = 7.4 Hz, 1H), 7.56−7.47 (m, 4H), 5.60 (s, 1H), 2.94−2.73 (m, 2H), 1.59−1.47 (m, 2H), 1.38−1.30 (m, 2H), 0.87 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 189.1, 141.3, 134.9, 134.5, 134.5, 132.2, 129.0, 129.0, 128.9, 70.7, 32.6, 30.8, 21.8, 13.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C18H19O3S2ClNa 405.0356; found 405.0352. 1-Phenyl-2-(phenylsulfonyl)-2-(phenylthio)ethan-1-one (3z). White solid (41.6 mg, 57%). 1H NMR (500 MHz, CDCl3) δ 8.01 (dd, J = 8.3, 1.1 Hz, 2H), 7.88 (dd, J = 8.3, 1.1 Hz, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.56 (t, J = 7.9 Hz, 2H), 7.52− 7.49 (m, 2H), 7.46 (t, J = 7.9 Hz, 2H), 7.37−7.33 (m, 1H), 7.33− 7.29 (m, 2H), 5.81 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 189.3, 136.3, 135.1, 134.5, 134.4, 133.6, 132.1, 130.8, 129.5, 129.4, 129.3, 128.9, 128.7, 75.6. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C20H16O3S2Na 391.0433; found 391.0440. 1-Phenyl-2-(phenylsulfonyl)-2-(p-tolylthio)ethan-1-one (3aa). White solid (43.4 mg, 57%). 1H NMR (500 MHz, CDCl3) δ 8.02 (dd, J = 8.4, 1.1 Hz, 2H), 7.87 (dd, J = 8.4, 1.1 Hz, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.61 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.9 Hz, 2H), 7.46 (t, J = 7.9 Hz, 2H), 7.37 (s, 2H), 7.11 (d, J = 8.0 Hz, 2H), 5.73 (s, 1H), 9453
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
Note
The Journal of Organic Chemistry 2.34 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 189.3, 140.0, 136.5, 135.2, 134.4, 134.3, 134.1, 130.8, 130.2, 129.2, 128.9, 128.7, 128.4, 75.8, 21.3. HRMS (ESI-TOF) m/z: [M + Na] + calcd for C21H18O3S2Na 405.0590; found 405.0599. 1-Phenyl-2-(phenylselanyl)-2-(phenylsulfonyl)ethan-1-one (3ab). Yellowish solid (30.6 mg, 37%). 1H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 7.4 Hz, 2H), 7.78 (d, J = 7.4 Hz, 2H), 7.65 (t, J = 7.5 Hz, 1H), 7.62−7.51 (m, 5H), 7.45−7.35 (m, 3H), 7.29 (d, J = 7.6 Hz, 2H), 5.79 (s, 1H). 13C NMR (126 MHz, CDCl3) δ 189.4, 137.0, 135.8, 135.0, 134.3, 134.2, 130.6, 129.8, 129.5, 128.9, 128.8, 128.7, 127.7, 68.1. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C20H16O3SSeNa 438.9878; found 438.9888. 1-Phenyl-2-(phenylsulfonyl)ethan-1-one (5). White solid. 1H NMR (500 MHz, Chloroform-d) δ 7.96−7.92 (m, 2H), 7.92−7.88 (m, 2H), 7.67 (t, J = 7.5 Hz, 1H), 7.63 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.8 Hz, 2H), 7.49 (t, J = 7.8 Hz, 2H), 4.75 (s, 2H).
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Lett. 2015, 17, 3402−3405. (i) Bag, R.; Sar, D.; Punniyamurthy, T. Copper(II)-Catalyzed Direct Dioxygenation of Alkenes with Air and N-Hydroxyphthalimide: Synthesis of β-Keto-N-alkoxyphthalimides. Org. Lett. 2015, 17, 2010−2013. (2) (a) Chen, F.; Wang, T.; Jiao, N. Recent Advances in TransitionMetal-Catalyzed Functionalization of Unstrained Carbon−Carbon Bonds. Chem. Rev. 2014, 114, 8613−9661. (b) Bag, R.; De, P. B.; Pradhan, S.; Punniyamurthy, T. Recent Advances in Radical Dioxygenation of Olefins. Eur. J. Org. Chem. 2017, 2017, 5424− 5438. (c) Plietker, B. RuO4-Catalyzed Ketohydroxylation of Olefins. J. Org. Chem. 2003, 68, 7123−7125. (d) Yang, D.; Huang, B.; Wei, W.; Li, J.; Lin, G.; Liu, Y.; Ding, J.; Sun, P.; Wang, H. Visible-light initiated direct oxysulfonylation of alkenes with sulfinic acids leading to βketosulfones. Green Chem. 2016, 18, 5630−5634. (e) Wei, W.; Liu, C.; Yang, D.; Wen, J.; You, J.; Suo, Y.; Wang, H. Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones. Chem. Commun. 2013, 49, 10239− 10241. (f) Yadav, V. K.; Srivastava, V. P.; Yadav, L. D. S. Rongalite® mediated highly regioselective aerobic hydroxysulfenylation of styrenes with disulfides: a convenient approach to β-hydroxy sulfides. Tetrahedron Lett. 2015, 56, 2892−2895. (g) Pagire, S. K.; Paria, S.; Reiser, O. Synthesis of β-Hydroxysulfones from Sulfonyl Chlorides and Alkenes Utilizing Visible Light Photocatalytic Sequences. Org. Lett. 2016, 18, 2106−2109. (h) Chawla, R.; Singh, A. K.; Yadav, L. D. S. K2S2O8-Mediated Aerobic Oxysulfonylation of Olefins into β-Keto Sulfones in Aqueous Media. Eur. J. Org. Chem. 2014, 2014, 2032− 2036. (3) (a) Kalmode, H. P.; Vadagaonkar, K. S.; Chaskar, A. C. Metalfree in situ sp3, sp2, and sp C−H functionalization and oxidative cross coupling with benzamidines hydrochloride: a promising approach for the synthesis of α-ketoimides. RSC Adv. 2014, 4, 60316−60326. (b) Zhao, W.; Montgomery, J. Cascade Copper-Catalyzed 1,2,3Trifunctionalization of Terminal Allenes. J. Am. Chem. Soc. 2016, 138, 9763−9766. (c) Pelz, N. F.; Morken, J. P. Modular Asymmetric Synthesis of 1,2-Diols by Single-Pot Allene Diboration/Hydroboration/Cross-Coupling. Org. Lett. 2006, 8, 4557−4559. (d) Ni, S.; Sha, W.; Zhang, L.; Xie, C.; Mei, H.; Han, J.; Pan, Y. NIodosuccinimide-Promoted Cascade Trifunctionalization of Alkynoates: Access to 1,1-Diiodoalkenes. Org. Lett. 2016, 18, 712−715. (e) Feng, Q.; Yang, K.; Song, Q. Highly selective copper-catalyzed trifunctionalization of alkynyl carboxylic acids: an efficient route to bis-deuterated β-borylated α,β-styrene. Chem. Commun. 2015, 51, 15394−15397. (4) For reviews, see: (a) Kondo, T.; Mitsudo, T. A. Metal-Catalyzed Carbon−Sulfur Bond Formation. Chem. Rev. 2000, 100, 3205−3220. (b) Mellah, M.; Voituriez, A.; Schulz, E. Chiral Sulfur Ligands for Asymmetric Catalysis. Chem. Rev. 2007, 107, 5133−5209. (c) Cremlyn, R. J. An Introduction to Organo-Sulfur Chemistry; Wiley & Sons: New York, 1996. (d) Li, Y.; Wang, M.; Jiang, X. Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis. ACS Catal. 2017, 7, 7587−7592. (e) Wang, D.; Cao, P.; Wang, B.; Jia, T.; Lou, Y.; Wang, M.; Liao, J. Copper(I)-Catalyzed Asymmetric Pinacolboryl Addition of N-Boc-imines Using a Chiral Sulfoxide−Phosphine Ligand. Org. Lett. 2015, 17, 2420−2423. (f) Feng, M.; Tang, B.; Liang, S.; Jiang, X. Sulfur Containing Scaffolds in Drugs: Synthesis and Application in Medicinal Chemistry. Curr. Top. Med. Chem. 2016, 16, 1200−1216. (g) Xiao, X.; Feng, M.; Jiang, X. New Design of a Disulfurating Reagent: Facile and Straightforward Pathway to Unsymmetrical Disulfanes by Copper-Catalyzed Oxidative CrossCoupling. Angew. Chem., Int. Ed. 2016, 55, 14121−14125. (5) (a) Giles, D.; Prakash, M. S.; Ramseshu, K. V. E-J. Chem. 2007, 4, 428. (b) Hartman, I.; Gillies, A. R.; Arora, S.; Andaya, C.; Royapet, N.; Welsh, W. J.; Wood, D. W.; Zauhar, R. J. Application of Screening Methods, Shape Signatures and Engineered Biosensors in Early Drug Discovery Process. Pharm. Res. 2009, 26, 2247−2258. (c) Krapcho, J.; Turk, C. F. 4-[3-(Dimethylamino)propyl]-3,4-dihydro-2-(1-hydroxyethyl)-3-phenyl-2H-1,4-benzothiazine and related compounds. New class of antiinflammatory agents. J. Med. Chem. 1973, 16, 776−779.
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b01161. 1 H and 13C NMR spectra and XRD data (3a) (PDF) Crystallographic data (CIF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Chen-Ho Tung: 0000-0001-9999-9755 Zhenghu Xu: 0000-0002-3189-0777 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We are grateful for financial support from the Natural Science Foundation of China and Shandong province (nos. 21572118 and JQ201505), subject construction funds (104.205.2.5), and Tang scholar award of Shandong University.
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REFERENCES
(1) (a) Lu, Q.; Zhang, J.; Wei, F.; Qi, Y.; Wang, H.; Liu, Z.; Lei, A. Aerobic Oxysulfonylation of Alkenes Leading to Secondary and Tertiary β-Hydroxysulfones. Angew. Chem., Int. Ed. 2013, 52, 7156− 7159. (b) Samanta, S.; Donthiri, R. R.; Ravi, C.; Adimurthy, S. Phenyliodonium Diacetate Mediated Oxidative Functionalization of Styrenes with Molecular Oxygen: Synthesis of α-Oxygenated Ketones. J. Org. Chem. 2016, 81, 3457−3463. (c) Xia, X. F.; Zhu, S. L.; Gu, Z.; Wang, H.; Li, W.; Liu, X.; Liang, Y. M. Catalyst-Controlled Dioxygenation of Olefins: An Approach to Peroxides, Alcohols, and Ketones. J. Org. Chem. 2015, 80, 5572−5580. (d) Zhang, T. S.; Xiong, Y. J.; Hao, W. J.; Zhu, X. T.; Wang, S. L.; Li, G.; Tu, S. J.; Jiang, B. DDQ-Mediated Three-Component Dioxygenation of Alkenes. J. Org. Chem. 2016, 81, 9350−9355. (e) Su, Y.; Sun, X.; Wu, G.; Jiao, N. Catalyst-Controlled Highly Selective Coupling and Oxygenation of Olefins: A Direct Approach to Alcohols, Ketones, and Diketones. Angew. Chem., Int. Ed. 2013, 52, 9808−9812. (f) Andia, A. A.; Miner, M. R.; Woerpel, K. A. Copper(I)-Catalyzed Oxidation of Alkenes Using Molecular Oxygen and Hydroxylamines: Synthesis and Reactivity of α-Oxygenated Ketones. Org. Lett. 2015, 17, 2704− 2707. (g) Sun, X.; Li, X.; Song, S.; Zhu, Y.; Liang, Y. F.; Jiao, N. MnCatalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols. J. Am. Chem. Soc. 2015, 137, 6059−6066. (h) Lu, Q.; Liu, Z.; Luo, Y.; Zhang, G.; Huang, Z.; Wang, H.; Liu, C.; Miller, J. T.; Lei, A. Copper-/CobaltCatalyzed Highly Selective Radical Dioxygenation of Alkenes. Org. 9454
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
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The Journal of Organic Chemistry
sulfonylation of alkenes. Chem. Sci. 2017, 8, 2610−2615. (c) Wang, W.; Wei, F.; Ma, Y.; Tung, C.-H.; Xu, Z. Copper(I)-Catalyzed ThreeComponent Click/Alkynylation: One-Pot Synthesis of 5-Alkynyl1,2,3-triazoles. Org. Lett. 2016, 18, 4158−4161. (d) Yuan, H.; Nuligonda, T.; Gao, H.; Tung, C.-H.; Xu, Z. Copper-catalyzed carbene insertion into the sulfur−sulfur bond of benzenesulfonothioate. Org. Chem. Front. 2018, 5, 1371−1374. (10) (a) Yin, G.; Mu, X.; Liu, G. Palladium(II)-Catalyzed Oxidative Difunctionalization of Alkenes: Bond Forming at a High-Valent Palladium Center. Acc. Chem. Res. 2016, 49, 2413−2423. (b) Xie, Z.; Jia, J.; Liu, X.; Liu, L. Copper(II) Triflate-Catalyzed Aerobic Oxidative C-H Functionalization of Glycine Derivatives with Olefins and Organoboranes. Adv. Synth. Catal. 2016, 358, 919−925.
(d) Papastaikoudi, T. S.; Tsotinis, A.; Chinou, I.; Roussakis, C. Farmaco 1994, 49, 221. (e) Holland, H. L.; Brown, F. M.; Barrett, F.; French, J.; Johnson, D. V. J. Ind. Microbiol. Biotechnol. 2003, 30, 292. (f) Kumar, A.; Sharma, S.; Tripathi, V. D.; Srivastava, S. Synthesis of chalcones and flavanones using Julia−Kocienski olefination. Tetrahedron 2010, 66, 9445−9449. (g) Wnuk, S. F.; Rios, J. M.; Khan, J.; Hsu, Y. L. Stannyl Radical-Mediated Cleavage of π-Deficient Heterocyclic Sulfones. Synthesis of α-Fluoro Esters. J. Org. Chem. 2000, 65, 4169−4174. (h) Xu, X. B.; Lin, Z. H.; Liu, Y.; Guo, J.; He, Y. Stevens rearrangement of thioethers with arynes: a facile access to multi-substituted β-keto thioethers. Org. Biomol. Chem. 2017, 15, 2716−2720. (i) Rospondek, M. J.; Marynowski, L.; Góra, M. Novel arylated polyaromatic thiophenes: Phenylnaphtho[b]thiophenes and naphthylbenzo[b]thiophenes as markers of organic matter diagenesis buffered by oxidising solutions. Org. Geochem. 2007, 38, 1729−1756. (6) For reviews, see: (a) Trost, B. M. alpha.-Sulfenylated carbonyl compounds in organic synthesis. Chem. Rev. 1978, 78, 363−382. (b) Li, J.; Ji, K.; Zheng, R.; Nelson, J.; Zhang, L. Expanding the horizon of intermolecular trapping of in situ generated α-oxo gold carbenes: efficient oxidative union of allylic sulfides and terminal alkynes via C−C bond formation. Chem. Commun. 2014, 50, 4130− 4133. (c) Wang, H.; Wang, G.; Lu, Q.; Chiang, C. W.; Peng, P.; Zhou, J.; Lei, A. Catalyst-Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β-Keto Sulfides and Sulfones. Chem. Eur. J. 2016, 22, 14489−14493. (d) Trost, B. M. Some aspects of organosulfur-mediated synthetic methods. Acc. Chem. Res. 1978, 11, 453−461. (e) Zou, L.-H.; Priebbenow, D. L.; Wang, L.; Mottweiler, J.; Bolm, C. Copper-Catalyzed Synthesis of α-Thioaryl Carbonyl Compounds Through S-S and C-C Bond Cleavage. Adv. Synth. Catal. 2013, 355, 2558−2563. (f) Zhou, S. F.; Pan, X.; Zhou, Z. H.; Shoberu, A.; Zou, J. P. Air Oxidative Radical Hydroxysulfurization of Styrenes Leading to β-Hydroxysulfides. J. Org. Chem. 2015, 80, 3682− 3687. (g) Li, J.; Xie, F. F.; Wang, P. Q.; Wu, Q. Y.; Chen, W. D.; Ren, J. M.; Zeng, B. B. Copper(I)-mediated trifluoromethylthiolation of αbromoketone with element sulfur and (trifluoromethyl)trimethylsilane. Tetrahedron 2015, 71, 5520−5524. (h) Jiang, M.; Zhu, F. X.; Xiang, H. Y.; Xu, X.; Deng, L. F.; Yang, C. H. An efficient and practical approach to trifluoromethylthiolation of α-haloketones/ α-haloarylmethanes. Org. Biomol. Chem. 2015, 13, 6935−6939. (i) Huang, Y. J.; He, X.; Lin, X. X.; Rong, M. G.; Weng, Z. Q. Copper-Catalyzed Synthesis of α-Trifluoromethylthio-Substituted Ketones. Org. Lett. 2014, 16, 3284−3287. (j) Ivanova, M. V.; Bayle, A.; Besset, T.; Pannecoucke, X.; Poisson, T. Copper-Mediated [(Diethylphosphono)difluoromethyl]thiolation of α-Bromo Ketones. Eur. J. Org. Chem. 2017, 2017, 2475−2480. (7) (a) Curti, C.; Laget, M.; Carle, A. O.; Gellis, A.; Vanelle, P. Rapid synthesis of sulfone derivatives as potential anti-infectious agents. Eur. J. Med. Chem. 2007, 42, 880−884. (b) Trost, B. M.; Salzmann, T. N.; Hiroi, K. New synthetic reactions. Sulfenylations and dehydrosulfenylations of esters and ketones. J. Am. Chem. Soc. 1976, 98, 4887−4902. (8) (a) Vaquer, A. F.; Frongia, A.; Secci, F.; Tuveri, E. Disulfidebased metal-free α-sulfanylation of ketones. RSC Adv. 2015, 5, 96695−96704. (b) Dias, R. M.; Burtoloso, A. C. Catalyst-Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β-Keto Thioethers. Org. Lett. 2016, 18, 3034−3037. (c) Cadu, A.; Watile, R. A.; Biswas, S.; Orthaber, A.; Sjoberg, P. J.; Samec, J. S. OnePot Synthesis of Keto Thioethers by Palladium/Gold-Catalyzed Click and Pinacol Reactions. Org. Lett. 2014, 16, 5556−5559. (d) Biswas, S.; Dahlstrand, C.; Watile, R. A.; Kalek, M.; Himo, F.; Samec, J. S. Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of α-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation. Chem. - Eur. J. 2013, 19, 17939−17950. (9) (a) Wang, W.; Peng, X.; Wei, F.; Tung, C.-H.; Xu, Z. Copper(I)Catalyzed Interrupted Click Reaction: Synthesis of Diverse 5-HeteroFunctionalized Triazoles. Angew. Chem., Int. Ed. 2016, 55, 649−653. (b) Li, H.; Shan, C.; Tung, C.-H.; Xu, Z. Dual gold and photoredox catalysis: visible light-mediated intermolecular atom transfer thio9455
DOI: 10.1021/acs.joc.8b01161 J. Org. Chem. 2018, 83, 9449−9455
