Enantioselective Organocatalytic Sulfenylation of β-Naphthols - The

Mar 29, 2018 - Journal of the American Chemical Society. Zheng, Cao, Chong, Han, Ding, Luo, Wang, Zhu, Zhou, and Ding. 2018 140 (32), pp 10374–10381...
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Article Cite This: J. Org. Chem. 2018, 83, 4730−4738

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Enantioselective Organocatalytic Sulfenylation of β‑Naphthols Jiao-Jiao Wang,† Hui Yang,† Bo-Bo Gou, Ling Zhou,* and Jie Chen* School of Chemistry & Material Science, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education of China, Northwest University, Xi’an 710127, China S Supporting Information *

ABSTRACT: An enantioselective sulfenylation of β-naphthols has been developed for the first time using a newly synthesized cinchona-derived thiourea as the catalyst and N(arylthio) succinimide (or phthalimide) as an electrophilic sulfur source. Various enantioenriched naphthalenones with an S-containing all-substituted stereocenter were prepared via a dearomatization strategy under mild reaction conditions.

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Scheme 1. Asymmetric Dearomatization of β-Naphthols

INTRODUCTION The organosulfur compounds are commonly occurring in natural products and drug molecules.1 Among them, chiral sulfides display numerous biological activities, which also serve as indispensable intermediates in synthetic organic chemistry.2 Consequently, developing the protocols for C−S bond formations has attracted a great deal of interest among researchers at the forefront of investigation and innovation in modern synthetic organic chemistry. To date, both transitionmetal-catalyzed3 and organo-catalyzed4 C−S bond formation reactions have been developed. In particular, an organocatalytic strategy has been proven to be efficient for the direct formation of stereogenic carbon centers bearing a sulfur atom, in which the Michael addition reactions with thiols (or thiophenols)5 and the sulfenylation reactions with electrophilic sulfur reagents6−12 are generally involved. Various active carbonyl compounds such as aldehydes,6 N-protected oxindoles,7 βketoesters,8 β-keto phosphonates,9 α-nitroesters,10 butyrolactone,11 as well as some alkenes12 were employed as substrates for asymmetric sulfenylation reactions. Although considerable efforts have been made for construction of C−S bonds enantioselectively, the direct sulfenylation still poses a challenge to researchers such as limited substrate scope. To continue our research interest in developing new sulfenylation reactions13 and dearomatization reaction of β-naphthols,14 we envisioned that electrophilic sulfur reagents may be used in the dearomatization reaction of β-naphthols to construct C−S bonds with a quaternary stereogenic center. Dearomatization reaction of β-naphthols have been studied intensively for a long time, which provided an efficient way to construct highly functionalized cyclohexadienones.15 Direct formation of C−O,16 C−C,14,17 C−N,18 and C−Cl19 bonds at the α-position of β-naphthols in catalytic asymmetric processes has been well studied by the dearomatization strategy (Scheme 1). However, to the best of our knowledge, there is no report on the construction of a C−S bond via such a strategy. Herein, we report an enantioselective sulfenylation of β-naphthols under the catalysis of cinchonaderived thiourea, providing an efficient preparation of © 2018 American Chemical Society

enantioenriched naphthalenones with an S-containing allsubstituted stereocenter.

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RESULTS AND DISCUSSION We initiated our studies by evaluating the reaction between 1methyl-2-naphthol (1a) and N-(phenylthio) phthalimide (2a) in CH2Cl2 at 25 °C in the presence of chiral phosphoric acid 4; however, no desired product was detected (Table 1, entry 1). On the contrary, the reaction proceeded smoothly by using cinchona-derived thiourea 5a as the catalyst, which afforded the expected product 3aa in 39% yield with an enantiomeric ratio (er) of 62.5:37.5. To improve the reactivity and the enantioselectivity, several cinchona-derived thiourea catalysts were investigated. An increase in enantioselectivity was realized when 4-methyl-substituted catalyst 5b was used (entry 3). Catalyst 5c bearing a strong electron-withdrawing group afforded a comparable er (entry 4 vs entry 3). Significantly, a clear increase in enantioselectivity was achieved when 4halogen-substituted catalyst 5d or 5e was measured (entries 5 and 6). In addition, the use of catalyst 5f which contains a 2,5dibromophenyl group could afford the desired product in 84.5:15.5 er (entry 7). However, no clear increase in enantioselectivity was observed when 2,4,6-tribromo-substituted catalyst 5g or 4-trityl substituted catalyst 5h was used (entries 8 and 9). Then, various solvents were screened, of which CH2Cl2 yielded the best results catalyzed by 5f (entries 10−14). Notably, reducing the reaction temperature to 0 °C Received: February 20, 2018 Published: March 29, 2018 4730

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry Table 1. Optimization of the Reaction Conditionsa

entry

S source

catalyst

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27

2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2aa 2b 2b 2b

4 5a 5b 5c 5d 5e 5f 5g 5h 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f 5f

additive (equiv)

solvent

T (°C)

time (h)

3

SPPh3 (0.5) K3PO4·3H2O (0.5) TFA (0.5) AlCl3 (0.5) HOCH2CH2OH (1.0) HOCH2CH2OH (3.0) HOCH2CH2OH (5.0) HOCH2CH2OH (3.0) HOCH2CH2OH (3.0) (+)-Taddol (3.0) (−)-Taddol (3.0)

CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 toluene CH3CN THF DMSO ClCH2CH2Cl CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2 CH2Cl2

25 25 25 25 25 25 25 25 25 25 25 25 25 25 0 40 25 25 25 25 25 25 25 25 25 25 25

84 70 70 78 75 72 72 72 72 75 75 75 75 75 72 72 75 75 75 75 75 75 75 75 75 75 75

3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3aa 3ab 3ab 3ab

yield (%)b

er (%)c

39 33 46 60 53 55 33 39 15 21 trace

62.5:37.5 76.5:23.5 77.5:22.5 81:19 84:16 84.5:15.5 64.5:35.5 74:26 72.5:27.5 68.5:31.5

33

63:37

42 21 33 trace

75:25 68.5:31.5 55.5:44.5

52 58 18 68 74 32 37

87.5:12.5 90:10 89.5:10.5 90.5:9.5 93.5:6.5 81.5:18.5 86:14

a c

Reactions were carried out with 1a (0.20 mmol), catalyst (0.02 mmol), and S source (0.24 mmol) in solvent (2.0 mL) under N2. bIsolated yields. The enantiomeric ratio (er) was determined by HPLC.

enantioselectivities (entries 1−6). β-Naphthols with an electron-donating group at the 6-position performed very well under standard conditions (entries 7 and 8), while the electronwithdrawing group returned a moderate yield and enantioselectivity (entry 9). To our delight, substrates with electrondeficient substituents or electron-donating substituents at the 7position of 2-naphthols were well tolerated; the corresponding products were all obtained in good yields and enantioselectivities (entries 10−13). Meanwhile, various 1,3-disubstituted-2naphthols were also investigated to explore the scope. The reactions proceeded smoothly with good yields and enantioselectivities, when different alkyl substituents were tested (entries 14, 15, 18). However, substrates with halogen groups at the C3-position yielded the corresponding products with a slight decrease in enantioselectivity (entries 16 and 17). In addition, various sulfur reagents were found to be tolerated in this asymmetric sulfenylation reaction (Table 3). Sulfur reagent with a methyl at the para position of the phenyl ring diminished the reaction (entry 1); the reason may be due

gave no desired product (entry 15). The use of a higher reaction temperature (40 °C) resulted in some lose of enantioselectivity, and without any increase in the catalytic efficiency (entry 16). Further optimization of the reaction by using additives was subsequently investigated (entries 17−23). Gratifyingly, a significant increase in enantioselectivity was observed when glycol was used as the additive (entries 21−23). An increase in the additive loading (from 3.0 equiv to 5.0 equiv) has a negative effect on the reaction conversion (entry 23). When chiral Taddols were used as the additives, no further improvement was observed (entries 26 and 27 vs entry 25). Finally, a 93.5:6.5 er was obtained by using compound 2b as the sulfur reagent (entry 25). To evaluate the efficiency of the newly established method, a series of β-naphthols with different substituents were examined under the optimized reaction conditions. As shown in Table 2, alkyl substituents including methyl, ethyl, propyl, allyl, and benzyl at the α-position of the naphthyl ring were all tolerated, giving the desired products in good yields and good 4731

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry Table 2. Substrate Scope of 2-Naphthols of 1a

entry

R1

R2

R3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

H H H H H H 6-MeO 6-Ph 6-Br 7-MeO 7-Ph 7-Br 7-CO2CH3 H H H H H H

Me Et n-Pr allyl 2-methylallyl benzyl Me Me Me Me Me Me Me Me Me Me Me allyl Me

H H H H H H H H H H H H H Me Et Cl Br Me Ph

3 yield (%)b 3ab 3b 3c 3d 3e 3f 3g 3h 3i 3j 3k 3l 3m 3n 3o 3p 3q 3r 3s

74 64 62 70 60 41 80 80 51 61 83 72 60 78 73 73 78 77 74

validate the synthetic utility of this newly developed protocol, several transformations of these products were carried out. Compound 3ab could be converted to the chiral alcohol 7 with excellent diastereoselectivity (>20:1). Additionally, treatment of 3ab with CH3MgBr yielded the chiral tertiary alcohol 8 with a high diastereoselectivity. All of these transformations were achieved efficiently without loss of enantiopurity. To elucidate the mechanism, two control experiments were conducted. As shown in Scheme 3. Sulfur reagent 9 without a carbonyl group resulted in 3aa with even no enantioselectivity (eq 1), suggesting that the carbonyl group in the sulfur source 2 is relevant not only to the reactivity but also to the enantiocontrol. When the additive glycol was protected with a methyl group, the desired product was obtained in only 20% yield together with a lower enantioselectivity (eq 2 vs Table 1, entry 25), indicating that the hydroxyl groups of glycol play an important role in the reaction. On the basis of the abovementioned experimental observations and previous research results,21 a plausible intermediate with a dual hydrogen bonding between the hydroxyl group of β-naphthol and the quinuclidine nitrogen is proposed (Figure 1).

er (%)c 93.5:6.5 86:14 92.5:7.5 90.5:9.5 91:9 90:10 91.5:8.5 90:10 85.5:14.5 85.5:14.5 90.5:9.5 86.5:13.5 87.5:12.5 93:7 92.5:7.5 85:15 85.5:14.5 92.5:7.5 90:10

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CONCLUSIONS In summary, we have developed an efficient catalytic enantioselective sulfenylation of β-naphthols for the first time by an organocatalytic dearomatization strategy. A series of enantioenriched naphthalenones with an S-containing allsubstituted stereocenter were prepared under mild reaction conditions. The practical transformations of the products reveal the potential synthetic utility of the reaction. Further investigations to better understand the mechanism and to develop new sulfenylation reactions are underway.

a

For the standard reaction conditions, see Table 1, entry 25. bIsolated yields. cThe er was determined by HPLC.

Table 3. Substrate Scope of Sulfur Reagents of 2a

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entry

Ar

product

yield (%)b

er (%)c

1 2 3 4 5 6 7 8 9

4-CH3-C6H4 4-F-C6H4 4-Cl-C6H4 4-Br-C6H4 3-Br-C6H4 2-Cl-C6H4 2-Br-C6H4 2,4-F2-C6H3 2,4-Cl2-C6H3

3ac 3ad 3ae 3af 3ag 3ah 3ai 3aj 3ak

45 78 80 64 79 43 32 86 59

87.5:12.5 91.5:8.5 91:9 90:10 91.5:8.5 91:9 87.5:12.5 92:8 90.5:9.5

EXPERIMENTAL SECTION

General. All reactions that required anhydrous conditions were carried by standard procedures under an argon atmosphere. Commercially available reagents were used as received. The solvents were dried by distillation over the appropriate drying reagents. Infrared spectra were recorded on a TENSOR 27FT-IR spectrophotometer and reported in wavenumbers (cm−1). 1H and 13CNMR spectra were recorded on a Varian (400 MHz) spectrometer. Chemical shifts (δ) are reported in ppm relative to TMS (δ 0.00) for the 1HNMR and to chloroform (δ 77.0) for the 13CNMR measurements. High resolution mass spectrawere obtained on an UltiMate 3000 spectrometer. Enantiomeric excesses were determined by HPLC analysis on Dionex UltiMate 3000 HPLC units, including the following instruments: pump, LPG-3400SD; detector, VWD-3100; column, Daicel Chiralpak IA, IB, IC or ID. Optical rotations were recorded on a Jasco DIP-1000 polarimeter. Reactions were followed with TLC (0.254 mm silica gel 60-F plates). Visualization was accomplished with UV light. Flash chromatography separations were performed on 200−300 mesh silica gel. Compounds 1a−s and 2. 1a−s22−25 and 226−28 were synthesized according to known literature procedures. Genera Procedure for Enantioselective Sulfenylation of βNaphthols. To a stirred solution of 2 (0.24 mmol), catalyst 5f (0.02 mmol), and glycol (0.6 mmol) in dry CH2Cl2 (2.0 mL) at 25 °C was added 1 (0.2 mmol) in one portion. The resulting mixture was stirred at 25 °C for 75 h. The solvent was removed under reduced pressure, and the residue was purified by flash column chromatography (petroleum ether/EtOAc) to yield the corresponding product 3. (S)-1-Methyl-1-(phenylthio)naphthalen-2(1H)-one (3aa). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (36 mg, 68% yield). [α]21 D +64.5 (c 1.0, CHCl3, 90.5:9.5 er); IR (KBr): 3431, 2926, 1663, 1493, 1234, 1155, 830, 748, 690 cm−1; 1H NMR (400 MHz, CDCl3):

a

Reactions were carried out with 1a (0.2 mmol), 2 (0.24 mmol), 5f (0.02 mmol), HOCH2CH2OH (0.6 mmol) in CH2Cl2 (2.0 mL) at 25 °C under N2. bIsolated yields. cThe er was determined by HPLC.

to that the electron-donating substituent reduced the electrophilicity of the S atom. Good yields and enantioselectivities were observed when sulfur reagents bearing electron-withdrawing groups at the para or meta position of the phenyl ring were used (entries 2−5). However, reagents bearing larger halogen groups at the ortho position of the phenyl ring offered a clear decrease in yields, presumably because of steric hindrance (entries 6−9). The absolute configuration of 3 was assigned on the basis of the X-ray crystallographic structure of 6,20 transformed from 3af by reduction and esterification (Scheme 2). To further 4732

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry Scheme 2. Transformations of Products

1657, 1471, 1261, 1065, 828, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 7.9 Hz, 1H), 7.47 (td, J = 7.7, 1.4 Hz, 1H), 7.38−7.32 (m, 2H), 7.28 (dd, J = 5.0, 2.4 Hz, 1H), 7.22 (td, J = 7.6, 1.7 Hz, 2H), 7.02 (ddd, J = 5.4, 4.3, 3.0 Hz, 2H), 6.25 (d, J = 9.9 Hz, 1H), 2.55− 2.37 (m, 2H), 0.58 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 194.3, 164.1 (d, J = 244.2 Hz), 143.0, 139.8, 138.8, 132.4 (d, J = 8.2 Hz), 131.1, 130.1, 129.7, 128.2, 128.1, 125.7, 124.0 (d, J = 3.9 Hz), 117.0 (d, J = 18.5 Hz), 115.8 (d, J = 24.1 Hz), 62.3, 28.1, 10.1; HRMS (ESI) calcd for C18H15FOSNa m/z [M + Na]+: 321.0720; found: 321.0712; HPLC (Daicel Chiralpak IE, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 13.9 min, t2 (minor) = 15.0 min. (S)-1-((2-Fluorophenyl)thio)-1-propylnaphthalen-2(1H)-one (3c). Purification by column chromatography with 35:1 petroleum ether/ EtOAc as the eluent gave the product as a yellow liquid (39 mg, 62% yield). [α]23 D +64.0 (c 1.0, CHCl3, 92.5:7.5 er); IR (KBr): 3433, 2961, 1659, 1476, 1223, 756 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 7.9 Hz, 1H), 7.46 (td, J = 7.7, 1.3 Hz, 1H), 7.38−7.30 (m, 2H), 7.28−7.25 (m, 2H), 7.20 (dd, J = 7.6, 1.6 Hz, 1H), 7.05−6.98 (m, 2H), 6.24 (d, J = 9.9 Hz, 1H), 2.50−2.30 (m, 2H), 0.96−0.84 (m, 2H), 0.79 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 194.4, 164.1 (d, J = 232.3 Hz), 143.0, 139.7, 139.3, 132.4 (d, J = 8.3 Hz), 130.8, 130.0, 129.6, 128.2, 128.0, 125.7, 124.0 (d, J = 4.0 Hz), 117.1 (d, J = 18.6 Hz), 115.8 (d, J = 24.0 Hz), 61.5, 37.3, 19.1, 14.2; HRMS (ESI) calcd for C19H17FOSNa m/z [M + Na]+: 335.0876; found: 335.0873; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 16.3 min, t2 (major) = 20.5 min. (S)-1-Allyl-1-((2-fluorophenyl)thio)naphthalen-2(1H)-one (3d). Purification by column chromatography with 40:1 petroleum ether/ EtOAc as the eluent gave the product as a yellow liquid (43 mg, 70% yield). [α]23 D +68.2 (c 1.0, CHCl3, 90.5:9.5 er); IR (KBr): 3431, 2926, 1623, 1471, 1261, 1223, 825, 758 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.39−7.27 (m, 4H), 7.23 (s, 1H), 7.04 (m, 2H), 6.25 (dd, J = 9.9, 1.6 Hz, 1H), 5.24 (ddd, J = 10.0, 8.6, 5.4 Hz, 1H), 4.86 (dd, J = 28.6, 13.7 Hz, 2H), 3.21 (ddd, J = 35.6, 14.0, 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 193.6, 164.1 (d, J = 249.4 Hz), 143.0, 139.7, 138.6, 132.6, 132.5, 130.8, 129.9, 129.7, 128.6, 128.1, 125.4, 124.1 (d, J = 4.1 Hz), 118.9, 116.9 (d, J = 18.4 Hz), 115.8 (d, J = 23.7 Hz), 60.7, 38.9; HRMS (ESI) calcd for C19H15FOSNa m/z [M + Na]+: 333.0720; found: 333.0721; HPLC (Daicel Chiralpak ID, i-PrOH/hexane = 8/92, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 13.6 min, t2 (minor) = 16.3 min. (S)-1-((2-Fluorophenyl)thio)-1-(2-methylallyl)naphthalen-2(1H)one (3e). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (39 mg, 60% yield). [α]22 D +66.9 (c 1.0, CHCl3, 91:9 er); IR (KBr): 3433, 2924, 1656, 1471, 1261, 1223, 831, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 7.8 Hz, 1H), 7.48−7.27 (m, 5H), 7.25 (m, 1H), 7.05 (dd, J = 12.1, 5.2 Hz, 2H), 6.30 (d, J = 9.9 Hz, 1H), 4.52 (s, 1H), 4.15 (s, 1H), 3.27 (dd, J = 37.8, 15.6 Hz, 2H), 1.38 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 192.9, 164.0 (d, J = 237.0 Hz), 142.9, 141.0, 140.0,

Scheme 3. Control Experiments

Figure 1. Proposed working model. δ 7.71 (d, J = 7.9 Hz, 1H), 7.46 (td, J = 7.7, 1.3 Hz, 1H), 7.36−7.30 (m, 2H), 7.20 (ddd, J = 9.9, 6.9, 2.6 Hz, 6H), 6.17 (d, J = 9.9 Hz, 1H), 1.83 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.5, 142.9, 141.6, 136.9, 130.1, 129.9, 129.9, 129.6, 129.3, 128.3, 127.8, 127.8, 125.0, 57.7, 21.1; HRMS (ESI) calcd for C17H14OSNa m/z [M + Na]+: 289.0658; found: 289.0653; HPLC (Daicel Chiralpak IB, i-PrOH/ hexane = 8/92, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 11.5 min, t2 (minor) = 15.5 min. (S)-1-((2-Fluorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ab). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (42 mg, 74% yield). [α]23 D +79.8 (c 0.33, CHCl3, 93.5:6.5 er); IR (KBr): 3423, 2924, 1656, 1475, 1261, 1065, 822, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.9 Hz, 1H), 7.44 (td, J = 7.6, 1.5 Hz, 1H), 7.40−7.31 (m, 2H), 7.30−7.19 (m, 3H), 7.10−6.98 (m, 2H), 6.25 (d, J = 9.9 Hz, 1H), 1.85 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.6, 164.1 (d, J = 249.4 Hz), 142.6, 140.5, 139.6, 132.5 (d, J = 8.5 Hz), 130.0, 130.0, 129.5, 128.2, 127.9, 125.1, 124.1 (d, J = 4.1 Hz), 117.3 (d, J = 18.5 Hz), 115.8 (d, J = 23.9 Hz), 58.0, 20.6; HRMS (ESI) calcd for C17H13FOSNa m/z [M + Na]+: 307.0563; found: 307.0552; HPLC (Daicel Chiralpak ID, i-PrOH/hexane = 10/90, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 16.3 min, t2 (minor) = 17.6 min. (S)-1-Ethyl-1-((2-fluorophenyl)thio)naphthalen-2(1H)-one (3b). Purification by column chromatography with 35:1 petroleum ether/ EtOAc as the eluent gave the product as a yellow liquid (38 mg, 64% yield). [α]23 D +51.4 (c 1.0, CHCl3, 86:14 er); IR (KBr): 3424, 2924, 4733

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry

liquid (38 mg, 61% yield). [α]20 D +36.8 (c 1.0, CHCl3, 85.5:14.5 er); IR (KBr): 3431, 2927, 1665, 1596, 1565, 1465, 1286, 1219, 1035, 836, 760 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.36 (tdd, J = 7.2, 5.1, 1.7 Hz, 1H), 7.28−7.18 (m, 4H), 7.05 (dd, J = 12.2, 5.0 Hz, 2H), 6.85 (dd, J = 8.4, 2.5 Hz, 1H), 6.14 (d, J = 9.8 Hz, 1H), 3.89 (s, 3H), 1.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.7, 164.1 (d, J = 249.4 Hz), 161.2, 142.8, 142.6, 139.6, 132.5 (d, J = 8.1 Hz), 131.1, 124.1 (d, J = 4.0 Hz), 123.2, 122.6, 117.6, 115.8 (d, J = 24.0 Hz), 114.2, 113.3, 58.2, 55.5, 21.0; HRMS (ESI) calcd for C18H15FO2SNa m/z [M + Na]+: 337.0669; found: 337.0664; HPLC (Daicel Chiralpak IC, iPrOH/hexane = 20/80, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 14.4 min, t2 (major) = 18.5 min. (S)-1-((2-Fluorophenyl)thio)-1-methyl-7-phenylnaphthalen2(1H)-one (3k). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (60 mg, 83% yield). [α]20 D −19.0 (c 1.0, CHCl3, 90.5:9.5 er); IR (KBr): 3441, 2924, 1657, 1469, 1219, 1068, 847, 754, 698 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.92 (d, J = 1.6 Hz, 1H), 7.64 (m, 2H), 7.55 (dd, J = 7.8, 1.8 Hz, 1H), 7.51−7.46 (m, 2H), 7.43−7.30 (m, 4H), 7.26 (m, 1H), 7.04 (t, J = 8.0 Hz, 2H), 6.28 (d, J = 9.8 Hz, 1H), 1.91 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 194.6, 164.1 (d, J = 249.5 Hz), 142.9, 142.3, 141.0, 140.1, 139.7, 132.6 (d, J = 8.5 Hz), 129.9, 129.0, 128.9, 128.1, 127.2, 126.9, 126.8, 125.0, 124.1 (d, J = 4.1 Hz), 117.5 (d, J = 18.6 Hz), 115.8 (d, J = 24.0 Hz), 58.3, 20.9; HRMS (ESI) calcd for C23H17FOSNa m/z [M + Na]+: 383.0876; found: 383.0874; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 20.0 min, t2 (major) = 26.5 min. (S)-7-Bromo-1-((2-fluorophenyl)thio)-1-methylnaphthalen2(1H)-one (3l). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (52 mg, 72% yield). [α]23 D +8.8 (c 1.0, CHCl3, 86.5:13.5 er); IR (KBr): 3443, 2924, 1659, 1468, 1381, 1223, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.82 (d, J = 1.9 Hz, 1H), 7.47 (dd, J = 8.1, 1.9 Hz, 1H), 7.42−7.36 (m, 1H), 7.22 (m, 2H), 7.12 (d, J = 8.1 Hz, 1H), 7.06 (t, J = 7.9 Hz, 2H), 6.27 (d, J = 9.9 Hz, 1H), 1.83 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 193.7, 164.1 (d, J = 246.3 Hz), 142.5, 141.5, 139.7, 132.8 (d, J = 8.5 Hz), 131.4, 131.2, 130.6, 128.8, 125.5, 124.6, 124.2 (d, J = 3.8 Hz), 117.0 (d, J = 18.1 Hz), 115.9 (d, J = 23.9 Hz), 57.7, 20.6; HRMS (ESI) calcd for C17H12BrFOSNa m/z [M + Na]+: 384.9668; found: 384.9658; HPLC (Daicel Chiralpak IC, i-PrOH/ hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 15.1 min, t2 (major) = 19.5 min. (S)-8-((2-Fluorophenyl)thio)-8-methyl-7-oxo-7,8-dihydronaphthalen-2-yl Acetate (3m). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (41 mg, 60% yield). [α]20 D +7.9 (c 1.0, CHCl3, 87.5:12.5 er); IR (KBr): 3429, 2926, 1722, 1663, 1480, 1276, 1225, 1114, 858, 758 cm−1; 1H NMR (400 MHz, CDCl3): δ 8.37 (d, J = 1.5 Hz, 1H), 8.00 (dd, J = 7.9, 1.6 Hz, 1H), 7.41−7.36 (m, 1H), 7.34 (d, J = 7.9 Hz, 1H), 7.28 (d, J = 8.5 Hz, 1H), 7.23 (dd, J = 7.3, 1.3 Hz, 1H), 7.05 (t, J = 8.0 Hz, 2H), 6.35 (d, J = 9.9 Hz, 1H), 3.98 (s, 3H), 1.90 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.0, 166.3, 164.1 (d, J = 251.4 Hz), 141.2, 140.6, 139.8, 133.8, 132.8 (d, J = 8.2 Hz), 131.1, 129.4, 129.0, 127.1, 124.2 (d, J = 4.1 Hz), 117.0 (d, J = 20.6 Hz), 115.9 (d, J = 23.9 Hz), 57.9, 52.5, 20.4; HRMS (ESI) calcd for C19H15FO3SNa m/z [M + Na]+: 365.0618; found: 365.0620; HPLC (Daicel Chiralpak IB, iPrOH/hexane = 8/92, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 16.9 min, t2 (minor) = 21.9 min. (S)-1-((2-Fluorophenyl)thio)-1,3-dimethylnaphthalen-2(1H)-one (3n). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (46 mg, 78% yield). [α]23 D +127.2 (c 1.0, CHCl3, 93:7 er); IR (KBr): 3443, 2924, 1659, 1472, 1440, 1259, 821, 756 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 7.7 Hz, 1H), 7.43−7.24 (m, 3H), 7.19 (td, J = 7.6, 2.6 Hz, 2H), 7.10−6.98 (m, 3H), 2.04 (s, 3H), 1.85 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.7, 164.0 (d, J = 249.1 Hz), 139.8, 139.7, 139.0, 132.9, 132.5 (d, J = 8.3 Hz), 130.6, 128.8, 128.5, 128.2, 127.6, 124.0 (d, J = 3.9 Hz), 117.5 (d, J = 18.7 Hz), 115.7 (d, J = 24.0 Hz), 57.7, 20.6, 16.2; HRMS (ESI) calcd for C18H15FOSNa m/z [M +

139.0, 132.7 (d, J = 8.3 Hz), 130.2, 129.8, 129.7, 128.5, 128.1, 125.5, 124.1 (d, J = 3.9 Hz), 116.7 (d, J = 20.0 Hz), 115.8 (d, J = 24.0 Hz), 113.6, 60.6, 41.9, 23.7; HRMS (ESI) calcd for C20H17FOSNa m/z [M + Na]+: 347.0876; found: 347.0871; HPLC (Daicel Chiralpak IC, iPrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 17.0 min, t2 (major) = 18.6 min. (S)-1-Benzyl-1-((2-fluorophenyl)thio)naphthalen-2(1H)-one (3f). Purification by column chromatography with 40:1 petroleum ether/ EtOAc as the eluent gave the product as a yellow liquid (30 mg, 41% yield). [α]20 D +36.0 (c 1.0, CHCl3, 90:10 er); IR (KBr): 3438, 2924, 1654, 1470, 1222, 821, 754, 467 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 7.9 Hz, 1H), 7.45 (td, J = 7.7, 1.3 Hz, 1H), 7.39−7.27 (m, 3H), 7.17 (dd, J = 10.3, 5.4 Hz, 2H), 7.04 (ddd, J = 5.2, 3.9, 2.8 Hz, 2H), 7.00−6.94 (m, 3H), 6.77 (dd, J = 6.6, 2.9 Hz, 2H), 6.17 (d, J = 9.9 Hz, 1H), 3.88 (d, J = 13.9 Hz, 1H), 3.72 (d, J = 13.9 Hz, 1H); 13 C NMR (100 MHz, CDCl3): δ 194.0, 164.2 (d, J = 274.0 Hz), 143.4, 139.5, 139.1, 136.2, 132.4(d, J = 8.4 Hz), 130.7, 129.8, 129.8, 129.6, 129.2, 128.1, 127.9, 126.3, 125.5, 124.2(d, J = 3.8 Hz),117.3(d, J = 18.4 Hz), 115.8 (d, J = 23.7 Hz), 62.1, 41.5; HRMS (ESI) calcd for C23H17FOSNa m/z [M + Na]+: 383.0876; found: 383.0877; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 20.5 min, t2 (major) = 22.3 min. (S)-1-((2-Fluorophenyl)thio)-6-methoxy-1-methylnaphthalen2(1H)-one (3g). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (31 mg, 80% yield). [α]22 D +79.5 (c 1.0, CHCl3, 91.5:8.5 er); IR (KBr): 3441, 2924, 1654, 1598, 1469, 1271, 1221, 1029, 821, 756 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.65 (d, J = 8.7 Hz, 1H), 7.41− 7.33 (m, 1H), 7.24 (m, 2H), 7.06 (t, J = 7.6 Hz, 2H), 6.99 (dd, J = 8.7, 2.7 Hz, 1H), 6.80 (d, J = 2.7 Hz, 1H), 6.27 (d, J = 9.9 Hz, 1H), 3.85 (s, 3H), 1.81 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.3, 164.1 (d, J = 250.0 Hz), 159.4, 142.3, 139.8, 132.5 (d, J = 8.3 Hz), 132.1, 131.2, 129.2, 125.7, 124.1 (d, J = 4.0 Hz), 117.6 (d, J = 18.0 Hz), 115.8 (d, J = 24.0 Hz), 115.6, 114.3, 58.0, 55.5, 20.6; HRMS (ESI) calcd for C18H15FO2SNa m/z [M + Na]+: 337.0669; found: 337.0663; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 20/80, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 13.1 min, t2 (major) = 18.0 min. (S)-1-((2-Fluorophenyl)thio)-1-methyl-6-phenylnaphthalen2(1H)-one (3h). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (58 mg, 80% yield). [α]23 D +20.7 (c 1.0, CHCl3, 90:10 er); IR (KBr): 3427, 2925, 1660, 1470, 1259, 756, 696 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 8.2 Hz, 1H), 7.67 (dd, J = 8.1, 2.0 Hz, 1H), 7.61 (m, 2H), 7.50−7.44 (m, 3H), 7.42−7.35 (m, 2H), 7.33 (d, J = 9.9 Hz, 1H), 7.29−7.25 (m, 1H), 7.10−7.02 (m, 2H), 6.31 (d, J = 9.9 Hz, 1H), 1.88 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.4, 164.2 (d, J = 246.0 Hz), 142.6, 141.3, 139.8, 139.7, 139.2, 132.6 (d, J = 8.4 Hz), 130.4, 128.9, 128.6, 128.4, 128.1, 127.9, 127.0, 125.6, 124.1 (d, J = 4.1 Hz), 117.4 (d, J = 18.5 Hz), 115.9 (d, J = 23.8 Hz), 58.0, 20.6; HRMS (ESI) calcd for C23H17FOSNa m/z [M + Na]+: 383.0876; found: 383.0874; HPLC (Daicel Chiralpak IC, i-PrOH/ hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 17.8 min, t2 (major) = 23.1 min. (S)-6-Bromo-1-((2-fluorophenyl)thio)-1-methylnaphthalen2(1H)-one (3i). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (37 mg, 51% yield). [α]23 D +23.1 (c 1.0, CHCl3, 85.5:14.5 er); IR (KBr): 3433, 2924, 1664, 1471, 1259, 1078, 829, 758 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.56 (m, 2H), 7.42−7.34 (m, 2H), 7.26−7.20 (m, 1H), 7.16 (d, J = 9.9 Hz, 1H), 7.05 (t, J = 8.1 Hz, 2H), 6.28 (d, J = 9.9 Hz, 1H), 1.81 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 193.7, 164.0 (d, J = 249.6 Hz), 141.0, 139.6, 139.3, 132.8 (d, J = 8.4 Hz), 132.6, 131.8, 131.8, 129.5, 126.3, 124.2 (d, J = 3.9 Hz), 122.1, 117.0 (d, J = 18.4 Hz), 115.9 (d, J = 23.7 Hz), 57.7, 20.5; HRMS (ESI) calcd for C17H12BrFOSNa m/z [M + Na]+: 384.9668; found: 384.9666; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 19.8 min, t2 (major) = 26.5 min. (S)-1-((2-Fluorophenyl)thio)-7-methoxy-1-methylnaphthalen2(1H)-one (3j). Purification by column chromatography with 35:1 petroleum ether/EtOAc as the eluent gave the product as a colorless 4734

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry Na]+: 321.0720; found: 321.0713; HPLC (Daicel Chiralpak IB, iPrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 6.9 min, t2 (minor) = 7.7 min. (S)-3-Ethyl-1-((2-fluorophenyl)thio)-1-methylnaphthalen-2(1H)one (3o). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (46 mg, 73% yield). [α]22 D +120.2 (c 1.0, CHCl3, 92.5:7.5 er); IR (KBr): 3443, 2924, 1655, 1496, 1441, 1259, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 7.7 Hz, 1H), 7.41−7.28 (m, 3H), 7.22− 7.14 (m, 2H), 7.06−6.99 (m, 3H), 2.46 (m, 2H), 1.85 (s, 3H), 1.17 (t, J = 7.5 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 194.6, 164.0 (d, J = 251.1 Hz), 139.8, 139.7, 138.0, 137.4, 132.4 (d, J = 8.4 Hz), 130.6, 128.8, 128.7, 128.2, 127.6, 123.9 (d, J = 3.9 Hz), 117.6 (d, J = 18.6 Hz), 115.7 (d, J = 24.0 Hz), 57.7, 22.3, 20.9, 12.3; HRMS (ESI) calcd for C19H17FOSNa m/z [M + Na]+: 335.0876; found: 335.0876; HPLC (Daicel Chiralpak IB, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 5.6 min, t2 (minor) = 6.3 min. (S)-3-Chloro-1-((2-fluorophenyl)thio)-1-methylnaphthalen2(1H)-one (3p). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (46 mg, 73% yield). [α]20 D +101.4 (c 1.0, CHCl3, 85:15 er); IR (KBr): 3441, 2924, 1670, 1468, 1224, 895, 752, 594 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.49−7.34 (m, 4H), 7.23 (m, 2H), 7.12−7.05 (m, 2H), 1.90 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 187.4, 164.1 (d, J = 249.9 Hz), 140.0, 139.7, 139.2, 133.0 (d, J = 8.5 Hz), 130.2, 130.1, 129.5, 129.1, 128.7, 127.9, 124.3 (d, J = 3.9 Hz), 116.7 (d, J = 18.5 Hz), 115.9 (d, J = 24.0 Hz), 59.8, 20.6; HRMS (ESI) calcd for C17H12ClFOSNa m/z [M + Na]+: 341.0174; found: 341.0168; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 20/ 80, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 11.1 min, t2 (major) = 13.3 min. (S)-3-Bromo-1-((2-fluorophenyl)thio)-1-methylnaphthalen2(1H)-one (3q). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a colorless liquid (56 mg, 78% yield). [α]20 D +88.1 (c 1.0, CHCl3, 85.5:14.5 er); IR (KBr): 3438, 2924, 1661, 1470, 1259, 1223, 752 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.68 (s, 1H), 7.49 (td, J = 7.7, 1.3 Hz, 1H), 7.39 (m, 2H), 7.24−7.19 (m, 2H), 7.08 (t, J = 8.1 Hz, 2H), 1.91 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 187.4, 164.1 (d, J = 256.3 Hz), 143.9, 140.0, 139.6, 133.0 (d, J = 8.5 Hz), 130.3, 130.1, 129.1, 128.7, 128.0, 124.3 (d, J = 4.2 Hz), 121.9, 116.7 (d, J = 18.4 Hz), 115.9 (d, J = 23.8 Hz), 59.6, 20.9; HRMS (ESI) calcd for C17H12BrFOSNa m/z [M + Na]+: 384.9668; found: 384.9663; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 13.8 min, t2 (major) = 16.7 min. (S)-1-Allyl-1-((2-fluorophenyl)thio)-3-methylnaphthalen-2(1H)one (3r). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (50 mg, 77% yield). [α]23 D +134.3 (c 1.0, CHCl3, 92.5:7.5 er); IR (KBr): 3438, 2922, 1655, 1469, 1435, 1222, 918, 820, 756 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.67 (d, J = 7.8 Hz, 1H), 7.41−7.34 (m, 2H), 7.29 (td, J = 7.5, 1.1 Hz, 1H), 7.24−7.17 (m, 2H), 7.08−7.01 (m, 3H), 5.24 (ddt, J = 17.1, 10.2, 6.8 Hz, 1H), 4.93−4.79 (m, 2H), 3.27 (dd, J = 14.0, 6.6 Hz, 1H), 3.16 (dd, J = 14.0, 7.1 Hz, 1H), 2.03 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 193.6, 164.1 (d, J = 249.4 Hz), 139.9, 139.4, 137.7, 133.1, 132.8, 132.6 (d, J = 8.2 Hz), 131.4, 128.8, 128.8, 128.2, 128.1, 124.0 (d, J = 4.0 Hz), 118.8, 117.0 (d, J = 18.6 Hz), 115.8 (d, J = 23.8 Hz), 60.5, 38.7, 16.1; HRMS (ESI) calcd for C20H17FOSNa m/z [M + Na]+: 347.0876; found: 347.0870; HPLC (Daicel Chiralpak IA, i-PrOH/hexane = 5/95, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 12.8 min, t2 (minor) = 14.1 min. (S)-1-((2-Fluorophenyl)thio)-1-methyl-3-phenylnaphthalen2(1H)-one (3s). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (53 mg, 74% yield). [α]23 D +130.2 (c 1.0, CHCl3, 90:10 er); IR (KBr): 3443, 2922, 1657, 1468, 1223, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.59−7.53 (m, 2H), 7.45−7.29 (m, 7H), 7.25 (s, 1H), 7.11 (td, J = 7.5, 1.6 Hz, 1H), 6.99−6.91 (m, 2H), 1.95 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 193.6, 163.8 (d, J = 240.8 Hz), 140.3, 140.0, 139.8, 135.8, 135.2, 132.5 (d, J = 8.1 Hz),

130.6, 129.6, 129.5, 128.7, 128.3, 128.1, 128.1, 127.8, 123.9 (d, J = 3.9 Hz), 117.6 (d, J = 23.3 Hz), 115.7 (d, J = 24.0 Hz), 58.4, 21.0; HRMS (ESI) calcd for C23H17FOSNa m/z [M + Na]+: 383.0876; found: 383.0870; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 9.8 min, t2 (major) = 11.4 min. (S)-1-Methyl-1-(p-tolylthio)naphthalen-2(1H)-one (3ac). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (25 mg, 44% yield): [α]21 D +51.0 (c 0.5, CHCl3, 87.5:12.5 er); IR (KBr): 3445, 1653, 754, cm−1; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 7.9 Hz, 1H), 7.46 (td, J = 7.7, 1.4 Hz, 1H), 7.34 (tt, J = 7.4, 3.8 Hz, 1H), 7.28−7.24 (m, 1H), 7.22 (d, J = 9.9 Hz, 1H), 7.12 (d, J = 8.1 Hz, 2H), 7.05 (d, J = 8.0 Hz, 2H), 6.19 (d, J = 9.9 Hz, 1H), 2.33 (s, 3H), 1.81 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.3, 142.8, 141.5, 140.2, 137.1, 130.0, 129.4, 129.3, 128.0, 127.8, 126.7, 125.2, 118.4, 57.9, 21.4, 20.7; HRMS (ESI) calcd for C18H16OSNa m/z [M + Na]+: 303.0814; found: 303.0818; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 21.9 min, t2 (major) = 29.8 min. (S)-1-((4-Fluorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ad). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (44 mg, 78% yield): [α]20 D +99.8 (c 0.5, CHCl3, 91.5:8.5 er); IR (KBr): 3445, 2926, 1659, 1589, 1478, 1223, 1155, 829, 760, 523 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 7.9 Hz, 1H), 7.47 (td, J = 7.7, 1.4 Hz, 1H), 7.33 (td, J = 7.5, 1.2 Hz, 1H), 7.25−7.14 (m, 4H), 6.93−6.88 (m, 2H), 6.16 (d, J = 9.9 Hz, 1H), 1.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.6, 163.9 (d, J = 250.7 Hz), 143.2, 141.5, 139.1 (d, J = 8.8 Hz), 130.1, 130.0, 129.4, 128.1, 127.9, 125.6 (d, J = 3.4 Hz), 125.1, 115.7, 115.5, 57.8, 21.0; HRMS (ESI) calcd for C17H13FOSNa m/z [M + Na]+: 307.0563; found: 307.0565; HPLC (Daicel Chiralpak ID, iPrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 10.6 min, t2 (minor) = 11.9 min. (S)-1-((4-Chlorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ae). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (48 mg, 80% yield). [α]23 D +63.1 (c 1.0, CHCl3, 91:9 er); IR (KBr): 2926, 1664, 1479, 1389, 1244, 1091, 1014, 822, 754, 503 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 7.9 Hz, 1H), 7.47 (t, J = 7.1 Hz, 1H), 7.34 (t, J = 7.4 Hz, 1H), 7.26−7.22 (m, 2H), 7.18 (d, J = 7.1 Hz, 2H), 7.10 (d, J = 8.4 Hz, 2H), 6.16 (d, J = 9.9 Hz, 1H), 1.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.4, 143.2, 141.4, 138.1, 136.3, 130.1, 129.9, 129.4, 128.8, 128.7, 128.1, 127.9, 125.0, 57.9, 21.3; HRMS (ESI) calcd for C17H13ClOSNa m/z [M + Na]+: 323.0268; found: 323.0263; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 17.5 min, t2 (minor) = 19.0 min. (S)-1-((4-Bromophenyl)thio)-1-methylnaphthalen-2(1H)-one (3af). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (44 mg, 64% yield). [α]23 D +49.0 (c 1.0, CHCl3, 90:10 er); IR (KBr): 3431, 2926, 1661, 1572, 1477, 1249, 1073, 1009, 818, 759, 490 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.71 (d, J = 7.9 Hz, 1H), 7.47 (td, J = 7.7, 1.4 Hz, 1H), 7.36−7.31 (m, 3H), 7.26−7.18 (m, 2H), 7.06−7.01 (m, 2H), 6.16 (d, J = 9.9 Hz, 1H), 1.82 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.5, 143.3, 141.5, 138.3, 131.7, 130.1, 130.0, 129.5, 129.4, 128.2, 128.0, 125.1, 124.8, 57.9, 21.4; HRMS (ESI) calcd for C17H13BrOSNa m/z [M + Na]+: 366.9763; found: 366.9763; HPLC (Daicel Chiralpak IB, i-PrOH/hexane = 2/98, flow rate 0.8 mL/min, λ = 230 nm): t1 (major) = 14.8 min, t2 (minor) = 16.8 min. (S)-1-((3-Bromophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ag). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (54 mg, 79% yield). [α]23 D +54.4 (c 1.0, CHCl3, 91.5:8.5 er); IR (KBr): 3425, 2926, 1663, 1550, 1456, 1389, 1250, 829, 756, 687 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 7.9 Hz, 1H), 7.50−7.41 (m, 2H), 7.34 (td, J = 7.5, 1.1 Hz, 1H), 7.25−7.22 (m, 2H), 7.18 (d, J = 9.9 Hz, 1H), 7.12 (dt, J = 7.7, 1.4 Hz, 1H), 7.07 (t, J = 7.7 Hz, 1H), 6.16 (d, J = 9.9 Hz, 1H), 1.85 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.6, 4735

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry

80%). Used in the next step without purification. The reaction was performed using (1S,2R)-1-((4-bromophenyl)thio)-1-methyl-1,2-dihydronaphthalen-2-ol (0.16 mmol), 3,5-dinitrobenzoyl chloride (0.19 mmol), Et3N (0.19 mmol), and DMAP (0.016 mmol) in CH2Cl2 (1.5 mL) at 0 °C and then was warmed to room temperature. After workup, the reaction was quenched with a saturated solution of NaHCO3. The solution was extracted with CH2Cl2 (3 × 6 mL), washed with brine (8.0 mL), and dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure. The residue was purified by column chromatography to yield the corresponding product 6. Purification by column chromatography with 35:1 petroleum ether/ EtOAc as the eluent gave the product as a yellow soild (35 mg, 41% yield). [α]20 D −11.4 (c 0.5, CHCl3, 90:10 er); IR (KBr): 2924, 1761, 1472, 1260, 1229, 820, 752 cm−1; 1H NMR (400 MHz, CDCl3): δ 9.32 (s, 1H), 9.26 (s, 2H), 7.30 (m, 2H), 7.22 (d, J = 7.4 Hz, 2H), 7.14 (t, J = 7.3 Hz, 1H), 7.01 (d, J = 7.7 Hz, 1H), 6.92 (d, J = 8.1 Hz, 2H), 6.69 (d, J = 9.6 Hz, 1H), 6.12 (s, 1H), 6.02 (d, J = 9.6 Hz, 1H), 1.73 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 162.1, 148.6, 138.7, 136.2, 133.4, 131.4, 131.3, 130.4, 130.0, 129.7, 128.2, 127.9, 127.7, 126.0, 125.6, 123.7, 122.7, 78.9, 56.4, 24.4; HRMS (ESI) calcd for C24H17BrN2O6SNa m/z [M + Na]+: 562.9883; found: 562.9878; HPLC (Daicel Chiralpak ID, i-PrOH/hexane = 30/70, flow rate 0.6 mL/min, λ = 230 nm): t1 (major) = 19.6 min, t2 (minor) = 22.8 min. (1S,2R)-1-((2-Fluorophenyl)thio)-1-methyl-1,2-dihydronaphthalen-2-ol (7). To a stirred solution of 3ab (0.2 mmol) in dry THF (2.0 mL) at −40 °C was added LiAlH4 (0.24 mmol, 1.2 equiv). The mixture was stirred at this temperature for 2 h. The reaction was quenched with a saturated solution of NH4Cl (3.0 mL) at −40 °C and then was warmed to room temperature. The solution was extracted with CH2Cl2 (3 × 6 mL). The combined extracts were washed with brine (8.0 mL), dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography to yield the corresponding product 7. Purification by column chromatography with 35:1 petroleum ether/ EtOAc as the eluent gave the product as a colorless liquid (33 mg, 57% yield). [α]20 D −10.7 (c 1.0, CHCl3, 93.5:6.5 er); IR (KBr): 3423, 2924, 1460, 1195, 750 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.44 (d, J = 7.7 Hz, 1H), 7.25−7.14 (m, 3H), 6.98−6.89 (m, 1H), 6.86−6.80 (m, 1H), 6.75 (td, J = 7.6, 1.2 Hz, 1H), 6.57 (td, J = 7.5, 1.7 Hz, 1H), 5.87 (dd, J = 9.8, 2.5 Hz, 1H), 5.81−5.70 (m, 1H), 4.42 (dt, J = 11.0, 2.3 Hz, 1H), 3.26 (dd, J = 11.0, 2.9 Hz, 1H), 1.81 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 164.0 (d, J = 240.1 Hz), 139.5, 137.4, 132.8, 131.9, 131.5 (d, J = 8.4 Hz), 127.8, 127.8, 127.1, 126.8, 125.8, 123.6 (d, J = 4.1 Hz), 118.7 (d, J = 18.5 Hz), 115.1 (d, J = 24.4 Hz), 73.6, 59.9, 23.8; HRMS (ESI) calcd for C17H15FOSNa m/z [M + Na]+: 309.0720; found: 309.0722; HPLC (Daicel Chiralpak IA, i-PrOH/hexane = 5/95, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 10.5 min, t2 (major) = 11.2 min. (1S,2R)-1-((2-Fluorophenyl)thio)-1,2-dimethyl-1,2-dihydronaphthalen-2-ol (8). To a stirred solution of 3ab (0.2 mmol) in dry THF (2.0 mL) at −78 °C was added CH3MgBr (0.4 mmol, 2.0 equiv). The mixture was stirred at this temperature for 2 h. The reaction was quenched with a saturated solution of NH4Cl (3.0 mL) at 0 °C and then was warmed to room temperature. The solution was extracted with CH2Cl2 (3 × 6 mL). The combined extracts were washed with brine (8.0 mL), dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography to yield the corresponding product 8. Purification by column chromatography with 35:1 petroleum ether/ EtOAc as the eluent gave the product as a colorless liquid (32 mg, 53% yield). [α]20 D +118.2 (c 1.0, CHCl3, 93.5:6.5 er); IR (KBr): 3387, 2926, 1465, 1378, 1209, 756 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.23 (m, 2H), 7.18−7.12 (m, 2H), 6.98−6.89 (m, 1H), 6.86−6.81 (m, 1H), 6.75 (td, J = 7.6, 1.2 Hz, 1H), 6.50 (td, J = 7.5, 1.8 Hz, 1H), 5.85 (dd, J = 26.6, 9.8 Hz, 2H), 3.57 (s, 1H), 1.76 (s, 3H), 1.19 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 163.8 (d, J = 245.9 Hz), 139.7, 138.2, 137.9, 132.3, 131.5 (d, J = 8.2 Hz), 127.6, 127.4, 126.7, 125.6, 125.1, 123.5 (d, J = 3.8 Hz), 119.4 (d, J = 18.2 Hz), 115.1 (d, J = 24.3 Hz), 74.9, 64.4, 22.3, 18.7; HRMS (ESI) calcd for C18H17FOSNa m/z [M +

143.3, 141.4, 139.1, 135.3, 132.7, 132.4, 130.2, 130.0, 129.7, 129.4, 128.2, 128.0, 125.1, 121.8, 57.9, 21.4; HRMS (ESI) calcd for C17H13BrOSNa m/z [M + Na]+: 366.9763; found: 366.9767; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 14.7 min, t2 (major) = 15.6 min. (S)-1-((2-Chlorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ah). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (26 mg, 43% yield). [α]23 D +51.8 (c 0.5, CHCl3, 91:9 er); IR (KBr): 3441, 2926, 1663, 1449, 1249, 1034, 831, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 7.9 Hz, 1H), 7.47−7.39 (m, 2H), 7.34 (td, J = 7.5, 1.2 Hz, 1H), 7.28 (t, J = 1.6 Hz, 1H), 7.26−7.22 (m, 2H), 7.19 (dd, J = 7.7, 1.7 Hz, 1H), 7.12−7.07 (m, 1H), 6.28 (d, J = 9.9 Hz, 1H), 1.87 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 195.0, 142.6, 141.0, 140.8, 139.0, 131.0, 130.1, 129.9, 129.6, 129.5, 128.2, 128.0, 126.7, 125.4, 58.4, 21.2; HRMS (ESI) calcd for C17H13ClOSNa m/z [M + Na]+: 323.0268; found: 323.0269; HPLC (Daicel Chiralpak IC, i-PrOH/ hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 18.9 min, t2 (major) = 26.3 min. (S)-1-((2-Bromophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ai). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (22 mg, 32% yield). [α]23 D +62.6 (c 0.2, CHCl3, 87.5:12.5 er); IR (KBr): 3433, 2926, 1663, 1445, 1248, 1020, 832, 754 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 7.8 Hz, 1H), 7.61−7.57 (m, 1H), 7.44 (td, J = 7.7, 1.4 Hz, 1H), 7.33 (td, J = 7.5, 1.1 Hz, 1H), 7.28−7.23 (m, 2H), 7.17−7.12 (m, 3H), 6.29 (d, J = 9.9 Hz, 1H), 1.87 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.8, 142.6, 140.8, 138.4, 133.3, 132.1, 131.8, 130.8, 130.1, 130.1, 129.5, 128.2, 128.0, 127.3, 125.5, 58.5, 21.5; HRMS (ESI) calcd for C17H13BrOSNa m/z [M + Na]+: 366.9763; found: 366.9762; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/ 90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 17.7 min, t2 (major) = 23.0 min. (S)-1-((2,4-Difluorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3aj). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (52 mg, 86% yield). [α]23 D +52.6 (c 1.0, CHCl3, 92:8 er); IR (KBr): 3426, 2928, 1662, 1595, 1479, 1422, 1265, 1141, 1064, 966, 854, 836, 758 cm−1; 1 H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 7.8 Hz, 1H), 7.46 (td, J = 7.6, 1.4 Hz, 1H), 7.35 (td, J = 7.5, 1.2 Hz, 1H), 7.30−7.19 (m, 3H), 6.84−6.75 (m, 2H), 6.25 (d, J = 9.9 Hz, 1H), 1.83 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.4, 164.7 (d, J = 251.9 Hz), 164.6 (d, J = 252.1 Hz), 142.8, 140.8, 140.7, 140.3, 130.1, 130.0, 129.6, 128.4, 127.9, 125.1, 111.7 (dd, J = 21.4, 4.0 Hz), 104.4 (dd, J = 27.6, 25.6 Hz), 58.0, 20.4; HRMS (ESI) calcd for C17H12F2OSNa m/z [M + Na]+: 325.0469; found: 325.0466; HPLC (Daicel Chiralpak IC, i-PrOH/ hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 12.5 min, t2 (major) = 16.9 min. (S)-1-((2,4-Dichlorophenyl)thio)-1-methylnaphthalen-2(1H)-one (3ak). Purification by column chromatography with 30:1 petroleum ether/EtOAc as the eluent gave the product as a yellow liquid (39 mg, 59% yield). [α]23 D +47.2 (c 1.0, CHCl3, 90.5:9.5 er); IR (KBr): 3443, 2924, 1663, 1563, 1449, 1372, 1097, 1034, 812, 761 cm−1; 1H NMR (400 MHz, CDCl3): δ 7.74 (d, J = 7.8 Hz, 1H), 7.46 (td, J = 7.7, 1.4 Hz, 1H), 7.42 (d, J = 1.4 Hz, 1H), 7.36 (td, J = 7.5, 1.1 Hz, 1H), 7.30− 7.27 (m, 1H), 7.26 (d, J = 3.2 Hz, 1H), 7.11−7.09 (m, 2H), 6.26 (d, J = 9.9 Hz, 1H), 1.86 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 194.5, 142.8, 141.9, 140.5, 139.6, 136.6, 130.2, 130.1, 129.8, 129.6, 128.4, 128.2, 128.0, 127.1, 125.4, 58.5, 21.2; HRMS (ESI) calcd for C17H12Cl2OSNa m/z [M + Na]+: 356.9878; found: 356.9882; HPLC (Daicel Chiralpak IC, i-PrOH/hexane = 10/90, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 13.2 min, t2 (major) = 16.5 min. (1S,2R)-1-((4-Bromophenyl)thio)-1-methyl-1,2-dihydronaphthalen-2-yl 3,5-Dinitrobenzoate (6). The reaction was performed using 3af (0.2 mmol), THF (2.0 mL) and LiAlH4 (0.24 mmol, 1.2 equiv) at −40 °C. After workup, the reaction was quenched with a saturated solution of NH4Cl (3.0 mL) at −40 °C and then was warmed to room temperature. The solution was extracted with CH2Cl2 (3 × 6 mL). The combined extracts were washed with brine (8.0 mL), dried (Na2SO4), filtered, and concentrated in vacuo (56 mg, 0.16 mmol, 4736

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry Na]+: 323.0876; found: 323.0879; HPLC (Daicel Chiralpak IA, iPrOH/hexane = 5/95, flow rate 0.8 mL/min, λ = 230 nm): t1 (minor) = 9.1 min, t2 (major) = 10.2 min.

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2007, 46, 5369. (d) Zhao, G.-L.; Rios, R.; Vesely, J.; Eriksson, L.; Córdova, A. Organocatalytic Enantioselective Aminosulfenylation of α,β-Unsaturated Aldehydes. Angew. Chem., Int. Ed. 2008, 47, 8468. (e) Armstrong, A.; Emmerson, D. P. G. Enantioselective Synthesis of Allenamides via Sulfimide [2,3]-Sigmatropic Rearrangement. Org. Lett. 2009, 11, 1547. (7) (a) Han, Z.; Chen, W.; Dong, S.; Yang, C.; Liu, H.; Pan, Y.; Yan, L.; Jiang, Z. Highly Enantioselective Organocatalytic Sulfenylation of 3-Aryloxindoles. Org. Lett. 2012, 14, 4670. (b) Li, X.; Liu, C.; Xue, X.S.; Cheng, J.-P. Enantioselective Organocatalyzed Sulfenylation of 3Substituted Oxindoles. Org. Lett. 2012, 14, 4374. (c) Wang, C.; Yang, X.; Loh, C. C. J.; Raabe, G.; Enders, D. Organocatalytic, Asymmetric Synthesis of 3-Sulfenylated N-Boc-Protected Oxindoles. Chem. - Eur. J. 2012, 18, 11531. (d) Rueping, M.; Liu, X.; Bootwicha, T.; Pluta, R.; Merkens, C. Catalytic Enantioselective Trifluoromethylthiolation of Oxindoles Using Shelf-Stable N-(trifluoromethylthio)phthalimide and a Cinchona Alkaloid Catalyst. Chem. Commun. 2014, 50, 2508. (e) Zhu, X.-L.; Xu, J.-H.; Cheng, D.-J.; Zhao, L.-J.; Liu, X.-Y.; Tan, B. In Situ Generation of Electrophilic Trifluoromethylthio Reagents for Enantioselective Trifluoromethylthiolation of Oxindoles. Org. Lett. 2014, 16, 2192. (f) Huang, L.; Li, J.; Zhao, Y.; Ye, X.; Liu, Y.; Yan, L.; Tan, C.-H.; Liu, H.; Jiang, Z. Chiral Bicyclic Guanidine-Catalyzed Enantioselective Sulfenylation of Oxindoles and Benzofuran-2(3H)ones. J. Org. Chem. 2015, 80, 8933. (8) (a) Sobhani, S.; Fielenbach, D.; Marigo, M.; Wabnitz, T. C.; Jørgensen, K. A. Direct Organocatalytic Asymmetric α-Sulfenylation of Activated C-H Bonds in Lactones, Lactams, and β-Dicarbonyl Compounds. Chem. - Eur. J. 2005, 11, 5689. (b) Fang, L.; Lin, A.; Dr, H. H. P.; Dr, C. Z. P. Highly Enantioselective Sulfenylation of βKetoesters: H-Bond Acceptor Catalysis. Chem. - Eur. J. 2009, 15, 7039. (c) Bootwicha, T.; Liu, X.; Pluta, R.; Atodiresei, I.; Rueping, M. NTrifluoromethylthiophthalimide: A Stable Electrophilic SCF3-Reagent and Its Application in the Catalytic Asymmetric Trifluoromethylsulfenylation. Angew. Chem., Int. Ed. 2013, 52, 12856. (d) Wang, X.; Yang, T.; Cheng, X.; Shen, Q. Enantioselective Electrophilic Trifluoromethylthiolation of β-Ketoesters: A Case of Reactivity and Selectivity Bias for Organocatalysis. Angew. Chem., Int. Ed. 2013, 52, 12860. (9) Lin, A.; Fang, L.; Zhu, X.; Zhu, C.; Cheng, Y. Organocatalytic Enantioselective Sulfenylation of β-Keto Phosphonates: A Convenient Approach to Construct Hetero-Quaternary Stereocenters. Adv. Synth. Catal. 2011, 353, 545. (10) Fang, L.; Lin, A.; Shi, Y.; Cheng, Y.; Zhu, C. Enantioselective Sulfenylation of α-Nitroesters Catalyzed by Diarylprolinols. Tetrahedron Lett. 2014, 55, 387. (11) (a) Singha Roy, S. J.; Mukherjee, S. “On Water” Catalytic Enantioselective Sulfenylation of Deconjugated Butyrolactams. Org. Biomol. Chem. 2017, 15, 6921. (b) Qiao, B.; Liu, X.; Duan, S.; Yan, L.; Jiang, Z. Highly Enantioselective Organocatalytic α-Sulfenylation of Azlactones. Org. Lett. 2014, 16, 672. (c) Xu, M.; Qiao, B.; Duan, S.; Liu, H.; Jiang, Z. Highly Enantioselective α-Sulfenylation of 5Hoxazol-4-ones to N-(sulfanyl)succinimides. Tetrahedron 2014, 70, 8696. (12) (a) Denmark, S. E.; Kornfilt, D. J. P.; Vogler, T. Catalytic Asymmetric Thiofunctionalization of Unactivated Alkenes. J. Am. Chem. Soc. 2011, 133, 15308. (b) Denmark, S. E.; Jaunet, A. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. J. Am. Chem. Soc. 2013, 135, 6419. (c) Li, L.; Li, Z.; Huang, D.; Wang, H.; Shi, Y. Chiral Phosphoric Acid Catalyzed Enantioselective Sulfamination of Amino-Alkenes. RSC Adv. 2013, 3, 4523. (d) Denmark, S. E.; Chi, H. M. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. Mechanistic Aspects: A Remarkable Case of Negative Catalysis. J. Am. Chem. Soc. 2014, 136, 3655. (e) Denmark, S. E.; Jaunet, A. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins. Preparative and Stereochemical Aspects. J. Org. Chem. 2014, 79, 140. (13) Dong, Y.-T.; Jin, Q.; Zhou, L.; Chen, J. N-Heterocyclic Carbene Catalyzed Sulfenylation of α,β-Unsaturated Aldehydes. Org. Lett. 2016, 18, 5708.

ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b00487. Copies of 1H NMR, 13C NMR, and HPLC spectra for all products, and X-ray crystallographic data (PDF) X-ray crystallographic data for compound 6 (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (L.Z.). *E-mail: [email protected] (J.C.). ORCID

Ling Zhou: 0000-0002-6805-2961 Author Contributions †

These authors contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (NSFC-21672170) and the Key Science and Technology Innovation Team of Shaanxi Province (2017KCT-37) for financial support.

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REFERENCES

(1) (a) Kharasch, N.; Meyers, C. Y. The Chemistry of Organic Sulfur Compounds. Science 1967, 158, 250. (b) Nudelman, A. The Chemistry of Optically Active Sulfur Compounds-Part IV. Phosphorus Sulfur Relat. Elem. 1980, 9, 1−79. (2) (a) Trost, B. M. α-Sulfenylated Carbonyl Compounds in Organic Synthesis. Chem. Rev. 1978, 78, 363. (b) Zeng, J.-L.; Yu, S.-B.; Cao, Z.; Yang, D.-W. Preparation of S-Containing Aminophosphine and Phosphoramidite Ligands and Their Applications in Enantioselective C-C Bond Forming Reactions. Catal. Lett. 2010, 136, 243. (3) For selected reviews, see: (a) Kondo, T.; Mitsudo, T.-a. MetalCatalyzed Carbon-Sulfur Bond Formation. Chem. Rev. 2000, 100, 3205. (b) Beletskaya, I. P.; Ananikov, V. P. Transition-Metal-Catalyzed C-S, C-Se, and C-Te Bond Formation via Cross-Coupling and AtomEconomic Addition Reactions. Chem. Rev. 2011, 111, 1596. For selected examples, see: (c) Jereb, M.; Togni, A. Titanium(IV)Catalyzed Enantioselective Sulfenylation of β-Ketoesters. Org. Lett. 2005, 7, 4041. (d) Cai, Y.; Li, J.; Chen, W.; Xie, M.; Liu, X.; Lin, L.; Feng, X. Catalytic Asymmetric Sulfenylation of Unprotected 3Substituted Oxindoles. Org. Lett. 2012, 14, 2726. (4) Chauhan, P.; Mahajan, S.; Enders, D. Organocatalytic CarbonSulfur Bond-Forming Reactions. Chem. Rev. 2014, 114, 8807. (5) Lu, H.-H.; Zhang, F.-G.; Meng, X.-G.; Duan, S.-W.; Xiao, W.-J. Enantioselective Michael Reactions of β,β-Disubstituted Nitroalkenes: A New Approach to β2,2-Amino Acids with Hetero-Quaternary Stereocenters. Org. Lett. 2009, 11, 3946. (6) (a) Franzén, J.; Marigo, M.; Fielenbach, D.; Wabnitz, T. C.; Jørgensen, K. A.; Kjaersgaard, A. A General Organocatalyst for Direct α-Functionalization of Aldehydes: Stereoselective C-C, C-N, C-F, CBr, and C-S Bond-Forming Reactions. Scope and Mechanistic Insights. J. Am. Chem. Soc. 2005, 127, 18296. (b) Marigo, M.; Wabnitz, T. C.; Fielenbach, D.; Jørgensen, K. A. Enantioselective Organo Catalyzed αSulfenylation of Aldehydes. Angew. Chem., Int. Ed. 2005, 44, 794. (c) Armstrong, A.; Challinor, L.; Moir, J. H. Exploiting Organocatalysis: Enantioselective Synthesis of Vinyl Glycines by Allylic Sulfimide [2,3]-Sigmatropic Rearrangement. Angew. Chem., Int. Ed. 4737

DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738

Article

The Journal of Organic Chemistry (14) Li, X.-Q.; Yang, H.; Wang, J.-J.; Gou, B.-B.; Chen, J.; Zhou, L. Asymmetric Arylative Dearomatization of β-Naphthols Catalyzed by a Chiral Phosphoric Acid. Chem. - Eur. J. 2017, 23, 5381. (15) For selected reviews, see: (a) Pape, A. R.; Kaliappan, K. P.; Kündig, E. P. Transition-Metal-Mediated Dearomatization Reactions. Chem. Rev. 2000, 100, 2917. (b) López Ortiz, F.; Iglesias, M. J.; Fernández, I.; Andújar Sánchez, C. M.; Ruiz Gómez, G. Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis. Chem. Rev. 2007, 107, 1580. (c) Roche, S. P.; Porco, J. A. Dearomatization Strategies in the Synthesis of Complex Natural Products. Angew. Chem., Int. Ed. 2011, 50, 4068. (d) Zhuo, C.-X.; Zhang, W.; You, S.-L. Catalytic Asymmetric Dearomatization Reactions. Angew. Chem., Int. Ed. 2012, 51, 12662. (e) Zhuo, C.-X.; Zheng, C.; You, S.-L. Transition-Metal-Catalyzed Asymmetric Allylic Dearomatization Reactions. Acc. Chem. Res. 2014, 47, 2558. (f) Sun, W.; Li, G.; Hong, L.; Wang, R. Asymmetric Dearomatization of Phenols. Org. Biomol. Chem. 2016, 14, 2164. (g) Wu, W.-T.; Zhang, L.; You, S.-L. Catalytic Asymmetric Dearomatization (CADA) Reactions of Phenol and Aniline Derivatives. Chem. Soc. Rev. 2016, 45, 1570. (h) You, S.-L., Ed. Dearomatization Reactions; Wiley-VCH: Weinheim, 2016. (16) (a) Oguma, T.; Katsuki, T. Iron-Catalyzed Asymmetric Tandem Spiro-Cyclization Using Dioxygen in Air as the Hydrogen Acceptor. Chem. Commun. 2014, 50, 5053. (b) Zhang, Y.; Liao, Y.; Liu, X.; Xu, X.; Lin, L.; Feng, X. Catalytic Asymmetric Hydroxylative Dearomatization of 2-Naphthols: Synthesis of Lacinilene Derivatives. Chem. Sci. 2017, 8, 6645. (17) For selected examples, see: (a) Zhuo, C.-X.; You, S.-L. Palladium-Catalyzed Intermolecular Asymmetric Allylic Dearomatization Reaction of Naphthol Derivatives. Angew. Chem., Int. Ed. 2013, 52, 10056. (b) Zhuo, C.-X.; You, S.-L. Palladium-Catalyzed Intermolecular Allylic Dearomatization Reaction of α-Substituted β-Naphthol Derivatives: Scope and Mechanistic Investigation. Adv. Synth. Catal. 2014, 356, 2020. (c) Wang, S.-G.; Liu, X.-J.; Zhao, Q.-C.; Zheng, C.; Wang, S.-B.; You, S.-L. Asymmetric Dearomatization of β-Naphthols through a Bifunctional-Thiourea-Catalyzed Michael Reaction. Angew. Chem., Int. Ed. 2015, 54, 14929. (d) Yang, D.; Wang, L.; Han, F.; Li, D.; Zhao, D.; Wang, R. Intermolecular Enantioselective Dearomatization Reaction of β-Naphthol Using meso-Aziridine: A Bifunctional In Situ Generated Magnesium Catalyst. Angew. Chem., Int. Ed. 2015, 54, 2185. (e) Yang, D.; Wang, L.; Kai, M.; Li, D.; Yao, X.; Wang, R. Application of a C-C Bond-Forming Conjugate Addition Reaction in Asymmetric Dearomatization of β-Naphthols. Angew. Chem., Int. Ed. 2015, 54, 9523. (f) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L. Asymmetric Dearomatization of Naphthols via a Rh-Catalyzed C(sp2)H Functionalization/Annulation Reaction. J. Am. Chem. Soc. 2015, 137, 4880. (g) Cheng, Q.; Wang, Y.; You, S.-L. Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives. Angew. Chem., Int. Ed. 2016, 55, 3496. (h) Wang, L.; Yang, D.; Li, D.; Wang, P.; Wang, K.; Wang, J.; Jiang, X.; Wang, R. MgII-Mediated Catalytic Asymmetric Dearomatization (CADA) Reaction of β-Naphthols with Dialkyl Acetylenedicarboxylates. Chem. - Eur. J. 2016, 22, 8483. (i) Alonso, A. D.; Baeza, A.; Chinchilla, R.; Gómez, C.; Guillena, G.; Pastor, M. I.; Ramón, J. D. Recent Advances in Asymmetric Organocatalyzed Conjugate Additions to Nitroalkenes. Molecules 2017, 22, 895. (18) (a) Wang, S.-G.; Yin, Q.; Zhuo, C.-X.; You, S.-L. Asymmetric Dearomatization of β-Naphthols through an Amination Reaction Catalyzed by a Chiral Phosphoric Acid. Angew. Chem. 2015, 127, 657. (b) Nan, J.; Liu, J.; Zheng, H.; Zuo, Z.; Hou, L.; Hu, H.; Wang, Y.; Luan, X. Direct Asymmetric Dearomatization of 2-Naphthols by Scandium-Catalyzed Electrophilic Amination. Angew. Chem., Int. Ed. 2015, 54, 2356. (c) Lian, X.; Lin, L.; Wang, G.; Liu, X.; Feng, X. Chiral N,N-Dioxide-Scandium(III)-Catalyzed Asymmetric Dearomatization of 2-Naphthols through an Amination Reaction. Chem. - Eur. J. 2015, 21, 17453. (19) Yin, Q.; Wang, S.-G.; Liang, X.-W.; Gao, D.-W.; Zheng, J.; You, S.-L. Organocatalytic Asymmetric Chlorinative Dearomatization of Naphthols. Chem. Sci. 2015, 6, 4179.

(20) CCDC 1815102 for compound 6. See the Supporting Information for details. (21) (a) Taylor, M. S.; Jacobsen, E. N. Asymmetric Catalysis by Chiral Hydrogen-Bond Donors. Angew. Chem., Int. Ed. 2006, 45, 1520. (b) Doyle, A. G.; Jacobsen, E. N. Small-Molecule H-Bond Donors in Asymmetric Catalysis. Chem. Rev. 2007, 107, 5713. (c) Connon, S. J. Asymmetric Catalysis with Bifunctional Cinchona Alkaloid-Based Urea and Thiourea Organocatalysts. Chem. Commun. 2008, 2499. (22) Pijper, D.; Jongejan, M. G. M.; Meetsma, A.; Feringa, B. L. Light-Controlled Supramolecular Helicity of a Liquid Crystalline Phase Using a Helical Polymer Functionalized with a Single Chiroptical Molecular Switch. J. Am. Chem. Soc. 2008, 130, 4541. (23) Oguma, T.; Katsuki, T. Iron-Catalyzed Dioxygen-Driven C-C Bond Formation: Oxidative Dearomatization of 2-Naphthols with Construction of a Chiral Quaternary Stereocenter. J. Am. Chem. Soc. 2012, 134, 20017. (24) Amézquita-Valencia, M.; Alper, H. PdI2-Catalyzed Regioselective Cyclocarbonylation of 2-Allyl Phenols to Dihydrocoumarins. Org. Lett. 2014, 16, 5827. (25) Li, S.; Xu, H.; Cui, S.; Wu, F.; Zhang, Y.; Su, M.; Gong, Y.; Qiu, S.; Jiao, Q.; Qin, C.; Shan, J.; Zhang, M.; Wang, J.; Yin, Q.; Xu, M.; Liu, X.; Wang, R.; Zhu, L.; Li, J.; Xu, Y.; Jiang, H.; Zhao, Z.; Li, J.; Li, H. Discovery and Rational Design of Natural-Product-Derived 2Phenyl-3,4-Dihydro-2H-Benzo[f ]chromen-3-Amine Analogs as Novel and Potent Dipeptidyl Peptidase 4 (DPP-4) Inhibitors for the Treatment of Type 2 Diabetes. J. Med. Chem. 2016, 59, 6772. (26) Song, Z.; Wu, Y.; Xin, T.; Jin, C.; Wen, X.; Sun, H.; Xu, Q.-L. The Rh(II)-Catalyzed Formal N-S Bond Insertion Reaction of Aryldiazoacetates into N-Phenyl-Sulfenyl Phthalimide. Chem. Commun. 2016, 52, 6079. (27) Xiong, F.; Lu, L.; Sun, T.-Y.; Wu, Q.; Yan, D.; Chen, Y.; Zhang, X.; Wei, W.; Lu, Y.; Sun, W.-Y.; Li, J. J.; Zhao, J. A Bioinspired and Biocompatible ortho-Sulfiliminyl Phenol Synthesis. Nat. Commun. 2017, 8, 15912. (28) Hostier, T.; Ferey, V.; Ricci, G.; Gomez Pardo, D.; Cossy, J. Synthesis of Aryl Sulfides: Metal-Free C-H Sulfenylation of ElectronRich Arenes. Org. Lett. 2015, 17, 3898.

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DOI: 10.1021/acs.joc.8b00487 J. Org. Chem. 2018, 83, 4730−4738