Air oxidative radical hydroxysulfurization of styrenes leading to β-hydroxysulfides

Article abstract of DOI:10.1021/acs.joc.5b00123

Air oxidative radical hydroxysulfurization of styrenes initiated by 0.5 mol % of tert-butyl hydroperoxide with arylthiols is described, and a new type of difunctionalization of alkenes was achieved.

Full text of DOI:10.1021/acs.joc.5b00123

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Note
Air Oxidative Radical Hydroxysulfurization
of Styrenes Leading to beta-Hydroxysulfides
Shao-Fang Zhou, Xiang-Qiang Pan, Zhi-Hao Zhou, Adedamola Shoberu, and Jian-Ping Zou
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b00123 • Publication Date (Web): 10 Mar 2015
Downloaded from http://pubs.acs.org on March 12, 2015
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Air Oxidative Radical Hydroxysulfurization of Styrenes Leading to βꢀ
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Hydroxysulfides
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ShaoꢀFang Zhou,a Xiangqiang Pan,*a ZhiꢀHao Zhou,a Adedamola Shoberu,a JianꢀPing Zou*a,b
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a Key Laboratory of Organic Synthesis of Jiangsu Province,,College of Chemistry and Chemical
Engineering, Soochow University, 199 Renai Street, Suzhou, Jiangsu 215123, China.
b Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China.
ABSTRACT: Air oxidative radical hydroxysulfurization of styrenes initiated by 0.5 mol % TBHP
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with arylthiols is described, a new type of difunctionalization of alkenes was achieved.
Difunctionalization has become a powerful tool in modern synthetic chemistry.1 The radical
difunctionalization reaction has attracted more attention in recent years because of its mild
conditions, high selectivity and convenient workꢀup.2 Thiolꢀoxygen cooxidation (TOCO) of olefins
first reported by Kharasch in 1951,3 is a wellꢀknown difunctionalization reaction, usually initiated by
UV irradiation or excess of peroxides. It has been widely applied to the synthesis of TOCO products
such as βꢀhydroperoxysulfides and βꢀhydroxysulfoxides, but not βꢀhydroxysulfides unless a
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reductant is added to the resultant compound in situ (Scheme 1, a). Hence, it is still a challenge to
prepare βꢀhydroxysulfides directly by TOCO reaction.
βꢀHydroxysulfides are important starting materials for the synthesis of higher functionalized
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organic molecules, pharmaceuticals, and natural products.7 One of the most straightforward
synthetic route to βꢀhydroxysulfides is the reaction of epoxides, commonly derived from alkenes,
with thiols in the presence of promoters and/or catalysts (Scheme 1, b).5, 8 These methods are useful
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but suffer from some drawbacks such as drastic reaction conditions, poor regioselectivity, lower
yields and undesirable byproducts.9 Recently, the methods of synthesizing βꢀhydroxysulfides via the
reaction of alkenes with thiols were developed by Rao and Kamal groups, these reactions were
conducted in βꢀcyclodextrin/H2O10 or ionic liquid [bmim][BF4]/H2O 11 medium through nonꢀradical
process (Scheme 1, c and d). Yadav group performed the same reaction utilizing eosin Y as an
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organophotoꢀredox catalyst in the visible light to afford the exclusive βꢀketosulfoxides. The
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experiment confirmed that the reaction proceeds via a radical pathway.
To the best of our
knowledge, no work on the direct oneꢀpot synthesis of βꢀhydroxysulfides via TOCO reaction has
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been reported. In continuation of our effort on difunctionalization of alkenes, herein, we report a
new radical hydroxysulfurization of styrenes for the direct synthesis of βꢀhydroxysulfides based on
the reaction of alkenes and arylthiols initiated by 0.5 mol % tertꢀbutyl hydroperoxide (TBHP)
(Scheme 1, e) .
Scheme 1. Protocols for Synthesis of βꢀHydroxysulfides
At the initial stage, the reaction of styrene (1a) with thiophenol (2a) in the presence of 0.5 mol %
tertꢀbutyl hydroperoxide (TBHP) was used as a model reaction. Solvents screening indicated that the
reaction in DMF afforded βꢀhydroxysulfide (3a) as a major product in 70 % yield, accompanied by a
byproducts βꢀoxosulfide (4a), benzaldehyde and diphenyldisulfide (Table 1, entry 5). Thus using
DMF as solvent, the ratio of 1a/2a, TBHP loading, temperature and time were screened (Table 1,
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entries 10ꢀ21), optimum reaction conditions were determined to be: styrene (1a, 1.0 equiv),
thiophenol (2a, 2 equiv) in DMF at 25oC for 48h (Table 1, entry 15) to afford the selective βꢀ
hydroxysulfide (3a) in 74% yield.
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Table 1. Optimization of the Reaction Conditionsa
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O
OH
SPh
SH
SPh
conditions
+
+
4a
1a
2a
3a
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Under the optimized reaction conditions, the reactions of a variety of substituted styrenes 1 with
thiophenol (2a) were carried out. Styrenes bearing Me, F and Cl groups on the phenyl ring were
tolerated to afford the selective βꢀhydroxysulfides in good yields although with prolonged reaction
time (Table 2, 3bꢀc, 3eꢀh). It is noteworthy that the reaction of 4ꢀmethoxystyrene (1d) gave the
desired product 3d in slightly low yield, this may be attributed to some of 1d being oxidized in the
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reaction. The reactions of styrenes bearing strong electronꢀwithdrawing groups such as CF3,
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COOCH3 and CN with 2a gave low yield of βꢀhydroxysulfides (Table 2, 3k, 3l and 3m), while no
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reaction was observed with the NO2 derivative (Table 2, 3n).
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Table 2. Reactions of Styrenes 1 and Thiophenol 2aa
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To evaluate the effect of
αꢀ or βꢀsubstituents of styrene on the reaction, CH3, Br and Ph
substituted styrenes were utilized for this purpose. The reactions of αꢀmethylstyrene (1o) and βꢀ
methylstyrene (1p) with 2a both afforded the expected βꢀhydroxysulfides 3o and 3p in 57% and 41%
yield, respectively (Table 3, entries 1ꢀ2). It was noted that the methyl substituent located at α or βꢀ
position of styrene has steric effect on the reaction leading to the decreased yield of products. Then
the reaction of αꢀbromostyrene (1q) with 2a was carried out, and βꢀoxosulfide 4q was isolated in
44% yield (Table 3, entry 3), while the reaction of βꢀbromostyrene (1r) with 2a gave the βꢀ
oxythioacetal 4r in 15% yield (Table 3, entry 4). Also, the reaction of αꢀphenylstyrene (1s) with 2a
was performed, and the corresponding βꢀhydroxysulfide 3s was isolated in 71% yield (Table 3, entry
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5). On the contrary, no reaction was observed for βꢀphenylstyrene (1t) (Table 3, entry 6). Based on
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the results aforementioned, using αꢀ or βꢀsubstituted (CH3, Br and Ph) styrenes as substrates,
different products or yields were obtained, which depended on both the kind of substituents and their
location. Finally, nonꢀconjugated terminal alkenes (1uꢀv) were used in place of styrene but no
reactions were observed (Table 3, entries 7ꢀ8).
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Table 3. Reactions of αꢀ and βꢀSubstituted Styrenes 1 with Thiophenol 2aa
With the promising results at hand, the reaction was extended to other arylthiols. The results
indicated that the kind of substituents and their location had an effect on the outcome of the reaction.
The reaction of oꢀtolylthiol (2b) with styrene (1a) gave the desired βꢀhydroxysulfide 3ab in 92%
yield, while the oꢀmethoxybenzenethiol (2c) afforded the βꢀoxosulfide 4ac in 16% yield, the pꢀ
methoxybenzenethiol (2e) and oꢀaminobenzenethiol (2f) gave no desired βꢀhydroxysulfides 3ae and
3af (Table 4). The arylthiols bearing F and Cl groups reacted with 1a to afford the expected βꢀ
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hydroxysulfides 3ag, 3ah and 3ai in moderate yields (Table 4), while the NO2 derivative did not
react (Table 4, 3aj). Also, no reactions were observed with pyridylthiol and furylthiol (Table 4, 3ak
and 3al).
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Table 4. Reactions of Styrene 1a with Arylthiols 2a,b
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Finally, the scaleꢀup reaction of 1a (10.4 g, 0.1 mol) with 2a (22.0 g, 0.2 mol) in DMF at room
temperature for 48 h in the presence of 0.5 mol % TBHP was performed, the expected product 3a
was obtained in 64% yield (14.7 g).
To confirm that the reaction proceeded via a radical pathway, TEMPO was added to the reaction
mixture of styrene (1a) with thiophenol (2a), only the product 5 was isolated, which was confirmed
to be 2,2,6,6ꢀtetramethylꢀ1ꢀ((phenylthio)oxy)piperidine formed from the reaction of TEMPO and
thiophenyl radical, but no βꢀhydroxysulfide (3a) was formed (Scheme 2). This result strongly
supported the free radical mechanism. On the basis of results obtained, a mechanism for the reaction
of styrenes 1 with thiophenol (2a) was proposed in Scheme 2. Thiyl radical 6 initiated by TBHP
selectively adds to the terminal C=C double bond of 1 to form intermediate radical 7. It reacts with
O2 to form peroxy radical 8, followed by reacting with 2a to form hydroperoxide 9 and thiyl radical 6
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is regenerated. 9 reacts with thiophenol (2a) to give radical 10, which then get hydrogen atom from
2a to afford product 3 and regenerate thiyl radical 6, which continues to drive the reaction further.
Scheme 2. Proposed Mechanism for the Reaction of Styrenes with Thiophenol
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In conclusion, a new type of difunctionalization of alkenes via the reaction of arylthiols with
styrenes has been developed. The reaction was initiated by 0.5 mol % TBHP at room temperature,
with air (O2) as sole oxidant to afford the hydroxysulfurization products in moderate to good yields.
The reaction can be effectively scaled up and product conveniently obtained in a oneꢀpot process.
This method is straightforward, requires no additives or other oxidant, and involves simple
manipulations. The βꢀhydroxysulfides obtained can be directly applied in syntheses of organic and
medicinal compounds, and can also be transformed into a variety of other useful functionalized
compounds.
EXPERIMENTAL SECTION
General Methods. 1H NMR (400 MHz) and 13C NMR (101 MHz) spectra were determined with
CDCl3 or DMSOꢀd6 as solvent and tetramethylsilane (TMS) as internal standard. Chemical shifts
were reported in ppm from internal TMS (δ); all coupling constants (J values) were reported in hertz
(Hz). Highꢀresolution mass spectra were recorded on a TOF machine (ESI). Column chromatography
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was performed with 300−400 mesh silica gel using flash column techniques. All of the reagents were
used directly as obtained commercially unless otherwise noted. All alkenes were purified by flash
column chromatography (Al2O3) before use.
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Preparation of 1ꢀArylꢀ2ꢀ(arylthio)ethanꢀ1ꢀol 3. Typical Procedure for the Preparation of 1ꢀ
Phenylꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3a). To a solution of dimethylformamide (DMF, 10 mL), styrene
(0.104 g, 1 mmol) and benzenethiol (0.22 g, 2 mmol) was added tꢀbutyl hydroperoxide (70%
aqueous solution, 0.7 ꢁL, 0.005 mmol), the mixture was stirred at room temperature in air for 48 h.
After the completion of the reaction, water (10 mL) was added to the reaction mixture, extracted
with ethyl acetate (10 mL × 3). The combined organic fractions were dried over anhydrous Na2SO4,
and concentrated under vacuum to yield the crude product, which was purified by column
chromatography (silica gel, petroleum ether/EtOAc = 40:1) to give 1ꢀphenylꢀ2ꢀ(phenylthio) ethanꢀ1ꢀ
ol (3a) .
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Scaleꢀup procedure for the Preparation of 1ꢀPhenylꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3a). To a solution
of DMF (200 mL), styrene (10.4 g, 0.1 mol) and benzenethiol (22.0 g, 0.2 mol) was added tꢀbutyl
hydroperoxide (70% aqueous solution, 0.05 g, 0.5 mmol), the mixture was stirred at room
temperature for 48 h. Then, water (100 mL) was added into the reaction mixture, and extracted with
ethyl acetate (100 mL × 3). The combined organic fractions were dried over anhydrous Na2SO4, and
o
vaporized under vacuum to give concentrated solution, which was cooled to 0 C, diphenyldisulfide
(PhSSPh) precipitated. The solid was filtered, the filtrate was concentrated and purified with
chromatography (silica gel, petroleum ether/EtOAc = 40:1) to afford 3a (yellow oil, 14.7 g, 64%
yield).
1ꢀPhenylꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3a)10. Yellow oil, 70% yield (161 mg). 1H NMR (400 MHz,
CDCl3): δ 7.33−7.10 (m, 10H), 4.62 (dd, J = 9.4, 3.5 Hz, 1H), 3.22 (dd, J = 13.8, 3.5 Hz, 1H), 3.00
(dd, J = 13.8, 9.4 Hz, 1H), 2.73 (s, 1H). 13C NMR (101 MHz, CDCl3): δ 142.2, 135.0, 130.2, 129.2,
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128.6, 128.0, 126.8, 125.9, 71.7, 44.0. MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C14H13S 213.1, found
213.1.
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2ꢀ(Phenylthio)ꢀ1ꢀ(pꢀtolyl)ethanꢀ1ꢀol (3b)10. Yellow oil, 80% yield (195 mg). 1H NMR (400 MHz,
CDCl3): δ 7.50−7.46 (m, 2H), 7.40−7.36 (m, 2H), 7.34−7.27 (m, 3H), 7.22 (d, J = 8.0 Hz, 2H), 4.76
(dd, J = 9.1, 3.9 Hz, 1H), 3.35 (dd, J = 13.7, 3.9 Hz, 1H), 3.18 (dd, J = 13.7, 9.1 Hz, 1H), 3.09 (s,
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1H), 2.42 (s, 3H). C NMR (101 MHz, CDCl3): δ 139.4, 137.7, 135.4, 130.1, 129.3, 129.2, 126.7,
126.0, 71.7, 43.8, 21.3. HRMS (CIꢀTOF) m/z: M+ Calcd for C15H16OS 244.0922, found 244.0933.
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2ꢀ(Phenylthio)ꢀ1ꢀ(oꢀtolyl)ethanꢀ1ꢀol (3c) . Yellow oil, 76% yield (185 mg). H NMR (400 MHz,
CDCl3): δ 7.59 (d, J = 7.4 Hz, 1H), 7.52−7.48 (m, 2H), 7.41−7.20 (m, 5H), 7.16 (d, J = 7.5 Hz, 1H),
4.97 (dd, J = 9.6, 3.1 Hz, 1H), 3.32 (dd, J = 13.9, 3.1 Hz, 1H), 3.07 (dd, J = 13.9, 9.6 Hz, 1H), 2.97
(s, 1H), 2.22 (s, 3H). 13C NMR (101 MHz, CDCl3): δ 140.2, 135.0, 134.5, 130.7, 130.5, 129.16,
127.7, 127.0, 126.5, 125.4, 68.3, 43.1, 18.9. HRMS (CIꢀTOF) m/z: M+ Calcd for C15H16OS 244.0922,
found 244.0925.
1ꢀ(4ꢀMethoxyphenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3d)10. Yellow oil, 62% yield (161 mg). H NMR
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(400 MHz, CDCl3): δ 7.46−7.42 (m, 2H), 7.38−7.22 (m, 5H), 6.91 (d, J = 8.7 Hz, 2H), 4.72 (dd, J =
9.2, 3.8 Hz, 1H), 3.82 (s, 3H), 3.31 (dd, J = 13.7, 3.9 Hz, 1H), 3.14 (dd, J = 13.7, 9.2 Hz, 1H), 2.94
(s, 1H). 13C NMR (101 MHz, CDCl3): δ 159.4, 135.1, 134.4, 130.1, 129.1, 127.2, 126.7, 114.0, 71.4,
55.3, 43.8. MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C15H15OS 243.1, found 243.1.
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1ꢀ(4ꢀFluorophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3e). Yellow oil, 71% yield (176 mg). H NMR (400
MHz, CDCl3): δ 7.46−7.42 (m, 2H), 7.39−7.23 (m, 5H), 7.15−6.99 (m, 2H), 4.72 (dd, J = 9.1, 3.8 Hz,
1H), 3.30 (dd, J = 13.8, 3.9 Hz, 1H), 3.20−2.95 (m, 2H, ꢀOH, ꢀCHꢀ). 13C NMR (101 MHz, CDCl3): δ
162.4 (d, J = 264.0 Hz), 138.0 (d, J = 3.1 Hz), 134.8, 130.3, 129.2, 127.7 (d, J = 8.1 Hz), 126.9,
115.4 (d, J = 21.5 Hz), 71.2, 44.0. HRMS (CIꢀTOF) m/z: M+ Calcd for C14H13FOS 248.0671, found
248.0679.
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1ꢀ(4ꢀChlorophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3f)10. Yellow oil, 79% yield (208 mg). H NMR
(400 MHz, CDCl3): δ 7.48−7.40 (m, 2H), 7.39−7.15 (m, 7H), 4.71 (dd, J = 9.3, 3.6 Hz, 1H), 3.30 (dd,
J = 13.8, 3.7 Hz, 1H), 3.07 (dd, J = 13.8, 9.3 Hz, 1H), 2.94 (s, 1H). 13C NMR (101 MHz, CDCl3): δ
140.6, 134.6, 133.6, 130.4, 129.2, 128.7, 127.2, 127.0, 71.0, 44.0. MS (ESIꢀTOF) m/z: (MꢀOH)+
Calcd for C14H12ClS 247.0, found 247.0.
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1ꢀ(2ꢀChlorophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3g). Yellow oil, 83% yield (219 mg). H NMR
(400 MHz, CDCl3): δ 7.70−7.66 (m, 1H), 7.48−7.52 (m, 2H), 7.38−7.28 (m, 4H), 7.29−7.21 (m, 2H),
5.13 (dd, J = 9.7, 2.7 Hz, 1H), 3.55 (dd, J = 14.0, 2.7 Hz, 1H), 3.03 (s, 1H), 2.92 (dd, J = 14.0, 9.7
Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 139.5, 134.3, 131.6, 130.4, 129.4, 129.1, 128.9, 127.2,
127.1, 126.9, 68.1, 42.2. HRMS (CIꢀTOF) m/z: M+ Calcd for C14H13ClOS 264.0376, found 264.0379.
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1ꢀ(3ꢀChlorophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3h) . Yellow oil, 83% yield (219 mg). H NMR
(400 MHz, CDCl3): δ 7.34−7.27 (m, 2H), 7.24−7.18 (m, 3H), 7.17−7.03 (m, 4H), 4.55 (dd, J = 9.3,
3.6 Hz, 1H), 3.17 (dd, J = 13.8, 3.6 Hz, 1H), 3.01 (s, 1H), 2.93 (dd, J = 13.8, 9.3 Hz, 1H). 13C NMR
(101 MHz, CDCl3): δ 144.3, 134.6, 134.5, 130.4, 129.8, 129.2, 128.1, 127.0, 126.1, 124.1, 71.1, 44.0.
HRMS (CIꢀTOF) m/z: M+ Calcd for C14H13ClOS 264.0376, found 264.0384.
1ꢀ(2ꢀBromophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3i). Yellow oil, 60% yield (185 mg). 1H NMR (400
MHz, CDCl3): δ 7.67 (dd, J = 7.8, 1.6 Hz, 1H), 7.56−7.48 (m, 3H), 7.42−7.31 (m, 3H), 7.31−7.24
(m, 1H), 7.16 (td, J = 7.7, 1.7 Hz, 1H), 5.08 (dd, J = 9.7, 2.6 Hz, 1H), 3.53 (dd, J = 14.0, 2.8 Hz,
1H), 3.15 (s, 1H), 2.90 (dd, J = 14.0, 9.7 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 141.1, 134.3,
132.8, 130.7, 129.3, 129.1, 127.9, 127.5, 127.0, 121.8, 70.4, 42.4. HRMS (CIꢀTOF) m/z: (M+H)+
Calcd for C14H14BrOS 308.9949, found 308.9936.
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1ꢀ(4ꢀBromophenyl)ꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3j)10. Yellow oil, 65% yield (201 mg). H NMR
(400 MHz, CDCl3): δ 7.50−7.45 (m, 2H), 7.44−7.40 (m, 2H), 7.39−7.30 (m, 2H), 7.24−7.30 (m, 1H),
7.24−7.17 (m, 2H), 4.68 (dd, J = 9.0, 3.8 Hz, 1H), 3.30 (s, 1H), 3.27 (dd, J = 13.8, 3.9 Hz, 1H), 3.08
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(dd, J = 13.8, 9.1 Hz, 1H). 13C NMR (101 MHz, CDCl3): δ 141.3, 134.8, 131.7, 130.3, 129.3, 127.7,
127.0, 121.8, 71.2, 43.8. MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C14H12BrS 291.0, found 291.0.
2ꢀ(Phenylthio)ꢀ1ꢀ(3ꢀ(trifluoromethyl)phenyl)ethanꢀ1ꢀol (3k) . Yellow oil, 54% yield (161 mg). 1H
NMR (400 MHz, CDCl3): δ 7.66 (s, 1H), 7.58−7.52 (m, 2H), 7.50−7.41 (m, 3H), 7.39−7.32 (m, 2H),
7.31−7.26 (m, 1H), 4.79 (dd, J = 9.2, 3.7 Hz, 1H), 3.34 (dd, J = 13.9, 3.8 Hz, 1H), 3.30 (s, 1H), 3.11
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(dd, J = 13.9, 9.2 Hz, 1H). C NMR (101 MHz, CDCl3): δ 143.2, 134.4, 130.8 (q, J = 32.3 Hz),
130.5, 129.3, 129.3, 129.3, 129.0, 127.1, 124.8 (q, J = 3.8 Hz), 122.8 (q, J = 3.8 Hz), 71.2, 44.0.
HRMS (CIꢀTOF) m/z: M+ Calcd for C15H13F3OS 298.0639, found 298.0652.
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Methyl 4ꢀ(1ꢀhydroxyꢀ2ꢀ(phenylthio)ethyl)benzoate (3l). Yellow oil, 52% yield (150 mg). H
NMR (400 MHz, CDCl3): δ 7.46−7.42 (m, 2H), 7.41−7.32 (m, 4H), 7.30−7.30 (m, 1H), 7.08−7.10
(m, 2H), 4.74 (dd, J = 9.5, 3.3 Hz, 1H), 3.33 (dd, J = 13.9, 3.5 Hz, 1H), 3.09 (dd, J = 13.9, 9.5 Hz,
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1H), 2.93 (s, 1H), 2.32 (s, 3H). C NMR (101 MHz, CDCl3): δ 169.6, 150.2, 140.0, 135.1, 130.1,
129.2, 127.1, 126.8, 121.7, 71.3, 43.7, 21.2. HRMS (CIꢀTOF) m/z: M+ Calcd for C16H16O3S
288.0820, found 288.0826.
4ꢀ(1ꢀHydroxyꢀ2ꢀ(phenylthio)ethyl)benzonitrile (3m)14. Yellow oil, 56% yield (143 mg). H NMR
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(400 MHz, DMSOꢀd6): δ 7.79 (d, J = 8.2 Hz, 2H), 7.58 (d, J = 8.2 Hz, 2H), 7.43−7.23 (m, 4H),
7.21− 7.11 (m, 1H), 5.93 (d, J = 4.7 Hz, 1H), 4.82 (dd, J = 11.1, 6.0 Hz, 1H), 3.25 (d, J = 6.2 Hz,
2H). 13C NMR (101 MHz, DMSOꢀd6): δ 154.7, 141.5, 137.2, 134.2, 133.3, 132.5, 130.9, 124.2,
115.1, 75.9, 46.2. MS (ESIꢀTOF) m/z: (M+H)+ Calcd for C15H14NOS 256.1, found 256.1.
2ꢀPhenylꢀ1ꢀ(phenylthio)propanꢀ2ꢀol (3o)15. Yellow oil, 57% yield (139 mg). 1H NMR (400 MHz,
CDCl3): δ 7.53 (d, J = 7.4 Hz, 2H), 7.42−7.28 (m, 4H), 7.35−7.26 (m, 3H), 7.26−7.20 (m, 1H), 3.60
(d, J = 13.3 Hz, 1H), 3.42 (d, J = 13.3 Hz, 1H), 3.06 (s, 1H), 1.69 (s, 3H). 13C NMR (101 MHz,
CDCl3): δ 146.3, 136.6, 130.0, 129.0, 128.3, 127.2, 126.5, 124.9, 74.1, 49.6, 29.4. MS (ESIꢀTOF)
m/z: (MꢀOH)+ Calcd for C15H15S 227.1, found 227.1.
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1ꢀPhenylꢀ2ꢀ(phenylthio)propanꢀ1ꢀol (3p)16. Yellow oil, 41% yield (combined yield of two
diastereomers) (dr = 86/14, determined by 1H NMR) (100 mg).
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Major diastereomer of 3p. 1H NMR (400 MHz, CDCl3): δ 7.42−7.24 (m, 10H), 4.81 (s, 1H), 3.60
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(qd, J = 7.0, 3.0 Hz, 1H), 2.88 (s, 1H), 1.21−1.18 (m, 3H). C NMR (101 MHz, CDCl3): δ 141.0,
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133.8, 132.4, 129.2, 128.2, 127.6, 127.4, 126.0, 73.3, 51.4, 13.2.
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Minor diastereomer of 3p. H NMR (400 MHz, CDCl3): δ 7.56−7.52 (m, 10H), 4.44 (d, J = 8.6
Hz, 1H), 3.49 (s, 1H), 3.41−3.29 (m, 1H), 1.13 (d, J = 6.9 Hz, 3H). 13C NMR (101 MHz, CDCl3): δ
140.9, 134.2, 133.7, 129.1 128.4, 128.1, 127.9, 127.1, 73.3, 52.7, 18.3.
MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C15H15S 227.1, found 227.1.
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1ꢀPhenylꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (4q). White solid, mp 58−60 °C. H NMR (400 MHz,
CDCl3): δ 8.02−7.92 (m, 2H), 7.69−7.59 (m, 1H), 7.53−7.46 (m, 2H), 7.44−7.38 (m, 2H), 7.40−7.21
(m, 3H), 4.31 (s, 2H). MS (ESIꢀTOF) m/z: (M+H)+ Calcd for C14H13 OS 229.1, found 229.1.
1ꢀPhenylꢀ2,2ꢀbis(phenylthio)ethanꢀ1ꢀol (4r). Yellow oil, 15% yield (50 mg). 1H NMR (400 MHz,
DMSOꢀd6): δ 8.07 (d, J = 7.2 Hz, 2H), 7.79−7.63 (m, 1H), 7.54 (t, J = 7.7 Hz, 2H), 7.48−7.40 (m,
4H), 7.38−7.34 (m, 6H), 6.68 (s, 1H). 13C NMR (101 MHz, DMSOꢀd6): δ 191.8, 134.8, 134.2, 133.6,
132.0, 129.5, 129.2, 128.9, 60.3. HRMS (CIꢀTOF) m/z: M+ Calcd for C20H16OS2 336.0643, found
336.0660.
1,1ꢀDiphenylꢀ2ꢀ(phenylthio)ethanꢀ1ꢀol (3s)15. Yellow oil, 78% yield (240 mg). H NMR (400
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MHz, CDCl3): δ 7.48−7.41 (m, 4H), 7.40−7.36 (m, 2H), 7.34−7.30 (m, 4H), 7.28−7.11 (m, 5H), 3.87
(s, 2H), 3.55 (s, 1H). 13C NMR (101 MHz, CDCl3): δ 145.2, 136.5, 130.3, 129.1, 128.3, 127.4, 126.7,
126.2, 77.7, 49.1. MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C20H17S 289.1, found 289.1.
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1ꢀPhenylꢀ2ꢀ(oꢀtolylthio)ethanꢀ1ꢀol(3ab). Yellow oil, 92% yield (230 mg). H NMR (400 MHz,
CDCl3): δ 7.47−7.33 (m, 6H), 7.27−7.18 (m, 3H), 4.79 (dd, J = 9.3, 3.6 Hz, 1H), 3.33 (dd, J = 13.6,
3.6 Hz, 1H), 3.16 (dd, J = 13.6, 9.3 Hz, 1H), 3.05 (s, 1H), 2.49 (s, 3H). 13C NMR (101 MHz, CDCl3):
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δ 142.4, 138.5, 134.4, 130.5, 129.3, 128.7, 128.6, 128.1, 126.7, 126.6, 126.0, 71.9, 43.1, 20.7. MS
(ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C15H15S 227.1, found 227.1.
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2ꢀ((2ꢀMethoxyphenyl)thio)ꢀ1ꢀphenylethanꢀ1ꢀol (4ac). Yellow oil, 16% yield (40 mg). H
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NMR (400 MHz, CDCl3): δ 7.98−7.94 (m, 2H), 7.62−7.56 (m, 1H), 7.50−7.44 (m, 2H), 7.37 (dd, J =
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7.6, 1.6 Hz, 1H), 7.30−7.24 (m, 1H), 6.90−6.86 (m, 2H), 4.25 (s, 2H), 3.87 (s, 3H). C NMR (101
MHz, CDCl3): δ 194.5, 158.4, 135.7, 133.3, 132.7, 129.1, 128.7, 128.6, 122.1, 121.1, 110.8, 55.7,
39.6. HRMS (CIꢀTOF) m/z: (M+H)+ Calcd for C15H15O2S 259.0793, found 259.0786.
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2ꢀ((2,6ꢀDimethylphenyl)thio)ꢀ1ꢀphenylethanꢀ1ꢀol (3ad). Yellow oil, 66% yield (160 mg). H
NMR (400 MHz, CDCl3): δ 7.41−7.30 (m, 5H), 7.23−7.16 (m, 3H), 4.66 (dd, J = 9.4, 3.6 Hz, 1H),
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3.10−3.04 (m, 2H, ꢀCH2ꢀ, OH), 2.97 (dd, J = 13.3, 9.4 Hz, 1H), 2.63 (s, 6H). C NMR (101 MHz,
CDCl3): δ 142.4, 142.0, 132.4, 128.1, 127.9, 127.4, 125.5, 72.2, 44.7, 21.7. MS (ESIꢀTOF) m/z: (Mꢀ
OH)+ Calcd for C16H17S 241.1, found 241.1.
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2ꢀ((2ꢀFluorophenyl)thio)ꢀ1ꢀphenylethanꢀ1ꢀol (3ag). Yellow oil, 48% yield (120 mg). H NMR
(400 MHz, CDCl3): δ 7.49 (td, J = 7.8, 1.8 Hz, 1H), 7.39−7.25 (m, 6H), 7.16−7.05 (m, 2H), 4.72 (dd,
J = 9.3, 3.4 Hz, 1H), 3.33 (dd, J = 13.7, 3.6 Hz, 1H), 3.10 (dd, J = 13.7, 9.3 Hz, 1H), 3.06 (s, 1H).
13C NMR (101 MHz, CDCl3): δ 161.5 (d, J = 245.6 Hz), 141.6, 132.9 (d, J = 1.4 Hz), 128.9 (d, J =
8.0 Hz), 128.1, 127.5, 125.4, 124.2 (d, J = 3.7 Hz), 121.2 (d, J = 17.7 Hz), 115.5 (d, J = 22.7 Hz),
71.5, 43.1 (d, J = 2.3 Hz). HRMS (CIꢀTOF) m/z: M+ Calcd for C14H13FOS 248.0671, found
248.0670.
2ꢀ((4ꢀFluorophenyl)thio)ꢀ1ꢀphenylethanꢀ1ꢀol (3ah). Yellow oil, 51% yield (130 mg). 1H NMR
(400 MHz, CDCl3): δ 7.49−7.44 (m, 2H), 7.41−7.31 (m, 5H), 7.11−7.04 (m, 2H), 4.74 (dd, J = 9.2,
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3.7 Hz, 1H), 3.36−3.25 (m, 1H), 3.13 (dd, J = 13.7, 9.2 Hz, 1H), 3.06 (s, 1H). C NMR (101 MHz,
CDCl3): δ 162.1 (d, J = 247.3 Hz), 142.1, 133.2 (d, J = 8.1 Hz), 130.0 (d, J = 3.4 Hz), 128.6, 128.1,
125.9, 116.3 (d, J = 21.9 Hz), 71.8, 45.1. MS (ESIꢀTOF) m/z: (MꢀOH)+ Calcd for C14H12FS 231.1,
found 231.0.
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2ꢀ((2ꢀChlorophenyl)thio)ꢀ1ꢀphenylethanꢀ1ꢀol(3ai). Yellow oil, 38% yield (100 mg). H NMR
(400 MHz, CDCl3): δ 7.48−7.32 (m, 7H), 7.29−7.22 (m, 1H), 7.20−7.14 (m, 1H), 4.79 (dd, J = 9.1,
3.7 Hz, 1H), 3.36 (dd, J = 13.5, 3.7 Hz, 1H), 3.18 (dd, J = 13.5, 9.2 Hz, 1H), 3.09 (s, 1H). 13C NMR
(101 MHz, CDCl3): δ 141.7, 134.3, 134.0, 129.8, 129.5, 128.2, 127.6, 127.0, 126.8, 125.4, 71.4,
42.3. HRMS (CIꢀTOF) m/z: M+ Calcd for C14H13ClOS 264.0376, found 264.0377.
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2,2,6,6ꢀTetramethylꢀ1ꢀ((phenylthio)oxy)piperidine (5). 1H NMR (400 MHz, CDCl3): δ 7.69 (d, J =
6.4 Hz, 2H), 7.44−7.42 (m, 2H), 7.40−7.36 (m, 1H), 1.95−1.75 (m, 1H), 1.74−1.30 (m, 15H),
1.00−0.80 (m, 2H). MS (ESIꢀTOF) m/z: (M+H)+ Calcd for C15H24NOS 266.2, found 266.2.
ASSOCIATED CONTENT
Supporting Information
The discussion and mechanism for the reactions of α−bromostyrene (1q), β−bromostyrene (1r)
and alkenes (1tꢀv) with thiophenol, as well as the reactions of oꢀmethoxythiophenol (2c), 4ꢀ
methoxyphenylthiol (2e), 2ꢀaminophenylthiol (2f), 4ꢀnitrophenylthiol (2j), 2ꢀpyridylthiol (2k) and 2ꢀ
1
furylthiol (2l) with styrene; H, 13C NMR spectra for compounds 3, 4 and 5. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*Eꢀmail: jpzou@suda.edu.cn; panxq@suda.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
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JPZ thanks the grant support by National Natural Science Foundation of China (Nos. 20772088,
21172163, 21472133) and the Priority Academic Program Development of Jiangsu Higher
Education Institutions for financial support.
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