Aerobic Nickel-Catalyzed Hydroxysulfonylation of Alkenes Using Sodium Sulfinates

Article abstract of DOI:10.1021/acs.joc.5b01176

Nickel-catalyzed hydroxysulfonylation of alkenes was achieved using sodium sulfinates under air atmosphere. The procedure enabled the selective synthesis of β-hydroxysulfones in good yields and suppressed the formation of β-ketosulfones. On the contrary, sulfonylation of alkynes with sodium sulfonates afforded only β-ketosulfones.

Full text of DOI:10.1021/acs.joc.5b01176

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Aerobic Nickel-catalyzed Hydroxysulfonylation
of Alkenes Using Sodium Sulfinates
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Nobukazu Taniguchi*
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, Japan
taniguti@fmu.ac.jp
cat.Ni-TEEDA
OH
NH4PF6
R
Ar2SO2Na
Ar1
+
R
Ar1
AcOH, DMF, H2O,
60 °C, air
SO2Ar2
R = H or Alkyl-
ABSTRACT. Nickel-catalyzed hydroxysulfonylation of alkenes was achieved using sodium
sulfinates under air atmosphere. The procedure enabled the selective synthesis of β-
hydroxysulfones in good yields, and suppressed the formation of β-ketosulfones. On the
contrary, sulfonylation of alkynes with sodium sulfonates afforded only β-ketosulfones.
Transition metal-catalyzed carbon−sulfur bond formation is an important methodology in
organic synthesis. Numerous efficient reactions have been reported.1 Compounds produced using
such methods have found widespread application as convenient reagents or intermediates.
In the synthesis of these organosulfur compounds, oxidation of sulfides2 or sulfonylation using
sulfonyl chlorides or its derivatives3,4 has been generally used to prepare sulfonyl compounds.
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However, these procedures are not well suited to the preparation of organosulfones bearing
functional groups. For instance, direct oxidation of β-hydroxysulfides cannot give β-
hydroxysulfones because of the oxidation of the hydroxy-group.
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Addition of sodium sulfinates to alkenes is considered the most appropriate method to
construct these compounds. Hydroxysulfonylation of styrene using sulfinic acids has recently
been reported (Scheme 1).5 The procedure affords β-hydoroxysulfones in good yields (a);
however, it requires excess sulfinic acids. Moreover, addition of PPh3 is often required for the
reduction of peroxides.
Similarly, reactions involving a strong oxidants such as CAN cannot produce hydroxysulfones
because of the formation of alkenyl sulfones (b).6 A similar result has been observed in a copper-
catalyzed reaction of sodium sulfinates with alkenes (c).7 Thus, a method for the convenient
preparation of β-hydroxysulfones from alkenes is needed but has not yet been developed.
Scheme 1. Sulfonylation of alkenes
(1) Sulfonylation of alkenes via oxidation of sulfinic acids
ArSO2H (2-10 equiv.)
OH
Py, O2(air)
(a)
SO2Ar
R
R
then PPh3
(2) Stoichiometric Sulfonylation of alkenes
ArSO2Na, CAN, NaI
(b)
SO2Ar
R
R
(3) Copper-catalyzed sulfonylation of alkenes
ArSO2Na(1.1 equiv.), KI
cat.CuX
SO2Ar
(c)
R
R
air
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Copper-catalyzed sulfonylation of alkenes or alkynes with sodium sulfinates affords alkenyl
sulfones with a trace amount of β-ketosulfones or β-hydroxysulfones as byproducts; however,
the procedure cannot produce these additives as major products. These substituents are
introduced through a radical process, and the origin of the hydroxy or keto groups is oxygen in
air.5,8 Consequently, control of the reaction is generally troublesome.9
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Solving this issue requires the use of reagents that promote both oxidation and reduction. One
approach is to exploit the characteristics of transition metals that can transfer a single electron,
and are easily oxidized or reduced by various materials or under certain conditions.10 Transition
metal catalysts are expected to enable both the oxidation of sulfonyl anion and the reduction of
peroxides (Scheme 2).
Therefore, in this study, the transition metal-catalyzed hydroxysulfonylation of alkenes was
investigated using transition metals other than copper.
From various experiments, it was observed that a nickel-catalyzed reaction of alkenes with
sodium sulfinates could produce the corresponding β-hydroxysulfones in excellent yields. Here,
it will be described the methodology of this reaction.
Scheme 2. Strategy
ArSO2Na
cat.M, air
Oxidation
•
OH
•
O2
ArSO2
Reduction
H+, cat.M
O2
•
SO2Ar
SO2Ar
SO2Ar
R
R
R
R
As shown in Table 1, a nickel-catalyzed reaction using styrene with sodium 4-toluenesulfinate
was initially surveyed to determine the suitable reaction conditions. When the reaction using
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NiBr2-bpy catalyst was conducted in DMF or AcOH, trace amounts of β-hydroxysulfones 2a and
β-ketosulfones 3a were observed (entries 1 and 2). However, the targeted reaction was not
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promoted at all. When H2O was added to these solvents, 2a was obtained in in 23−30% yields
(entries 3 and 4). However, a mixed solvent of DMF, AcOH and H2O produced unsatisfactory
results (entry 5). Notably, use of N,N,N’,N’-tetraethyl ethylenediamine (TEEDA) instead of bpy
furnished 2a in 51% yield (entry 6). Fortunately, when NH4PF6 was added, the yield of β-
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hydroxysulfone 2a was improved to 88% and the formation of β-ketosulfone 3a was suppressed
(entry 7). In contrast, other amine ligands did not promote the reaction satisfactorily, and
diphenylphosphinoethane (dppe) as a ligand failed to give 2a as a product (entries 8−10). Other
nickel catalysts were inferior to NiBr2 (entries 11−12). In the absence of the nickel catalyst, the
reaction scarcely proceeded (entry 13).
Table 1. Investigation of suitable condition
4-MeC6H4SO2Na,
OH
O
NiX2-L (1:1, 10 mol%)
Solvent, 60 °C
SO2C6H4Me-4
+
SO2C6H4Me-4
3a
Ph
Ph
Ph
1a
2a
Entry Ni-L
Solvent (mL)
AcOH
2a(%)
2a/3ab
80/20
91/9
1
2
3
NiBr2-bpy
-
DMF
-
AcOH/H2O
(0.2/0.2)
23
91/9
4
5
DMF/H2O
(0.2/0.2)
30
83/7
NiBr2-bpy
AcOH/DMF/H2O 30
(0.1/0.3/0.2)
81/19
6
7c
NiBr2-TEEDA
NiBr2-TEEDA
51
88
87/13
95/5
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8c
9c
NiBr2-
TMEDA
52
62
87/13
87/13
NiBr2-
(EtNHCH2)2
10c
11c
12c
NiBr2-dppe
-
80/20
87/13
78/22
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NiCl2-TEEDA
30
10
Ni(OAc)2-
TEEDA
13
None
16
83/17
aReaction conditions: A mixture of 1 (0.3 mmol), ArSO2Na (0.33 mmol) and NiX2-L (1:1, 5
mol%) in DMF (0.3 mL), H2O (0.2 mL) and AcOH (0.1 mL) was treated at 60 ºC.
bDetermined by 1H NMR analysis. cNH4PF6 (0.09 mmol) was added.
Numerous hydroxysulfonylations of alkenes were screened according to the aforementioned
procedure (Table 2). When the mixture of terminal aryl alkenes with sodium arenesulfinates was
treated with NiBr2-TEEDA catalyst in air, the corresponding β-hydroxysulfones 2 were obtained
in excellent yields, along with a trace amount of β-ketosulfones 3 (entries 1−14). Not only
terminal alkenes but also internal alkenes were used in the procedure (entries 15−18). Although
these cases did not afford β-ketosulfones, regio-isomers were often obtained. NMR analysis
revealed that these compounds were anti-adducts. Furthermore, reactions using trans- and cis-β-
methylstyrenes gave the same products (entries 15 and 16). These reactions apparently
proceeded via the same stable radical intermediate. On the contrary, use of 2-vinyl pyridine
resulted in hydrosulfonylation (entry 19). The reaction involving 4-octene was hardly promoted
(entry 20).
Table 2. Hyroxysulfonylation of alkenes
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ArSO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
NH4PF6
O
OH
+
SO2Ar
SO2Ar
R
R
R
DMF, AcOH, H2O, 60 °C
air
1
3
2
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Entry
1
(h) 2(%)
2/3b,c
2
OH
O2
S
18
88
95/5
2a
OH
O2
S
2
3
4
36
80
91/9
2b
OMe
OH
OH
OH
O2
S
36
36
70
76
91/9
2c
Cl
O2
S
100/0
2d
F
O2
S
5
6
7
36
18
18
75
70
71
95/5
95/5
91/9
2e
2f
OH
O2
S
OH
O2
S
2g
MeO
AcO
Cl
OH
OH
O2
S
8
9
18
18
68
62
65
100/0
91/91
83/17
2h
O2
S
2i
18
OH
O2
S
10
2j
F
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OH
O2
S
11
12
36
36
65
74
91/9
95/5
2k
2l
OH
Br
O2
S
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OH
O2
S
13
14
18
18
18
18
36
18
18
18
62
73
75
85
67
59
0f
91/9
-
2m
O2
S
HO
2n
2o
2o
2p
15d
16e
17
86/14c
86/14c
94/6c
100/0
-
OH
OH
OH
OH
OH
OH
O2
S
O2
S
O2
S
O2
S
18
2q
2r
O2
S
19
N
20
0
-
2s
O2S
aReaction conditions: A mixture of 1 (0.3 mmol), ArSO2Na (0.33 mmol), NH4PF6 (0.09 mmol)
and NiBr2-TEEDA (1:1, 5 mol%) in DMF (0.3 mL), H2O (0.2 mL) and AcOH (0.1 mL) was
treated at 60 ºC. bDetermined by 1H NMR analysis. cIn entries 15−17, the ratio of regio-isomers.
dcis-β-Methylstyrene was used. trans-β-Methylstyrene was used. Hydrosulfones were obtained
e
f
in 52% yield.
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To elucidate the reaction mechanism, some experiments were then performed. A reaction in
the absence of oxygen was examined (Scheme 3). When the mixture of styrene with sodium 4-
toluenesulfinate was treated under nitrogen atmosphere, the desired β-hydroxysulfone was not
obtained. Similarly, in the presence of TEMPO as radical scavenger, the reaction did not proceed
(Scheme 4).
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The necessity of water as a nucleophilic11 was also investigated (Scheme 5). The reaction in
the absence of water afforded β-hydroxysulfone and β-ketosulfone in 56% and 12% yields,
respectively.
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18
In addition, experiments involving H2 O revealed that the O isotope was not introduced as
the hydroxy oxygen atom (Scheme 6).
These results indicate that sulfonylation is necessary for oxygen and that the hydroxyl group is
introduced by the addition of oxygen.
A plausible reaction mechanism deduced from these results is illustrated in Figure 1. In the
first step, sodium sulfinate is oxidized by air in the presence of the nickel(II) catalyst.10b After the
formation of the sulfonyl radical 5, a reaction with alkenes gives a radical intermediate 6.
Sequentially, when 6 reacts with oxygen, an anion intermediate 7 is produced by the reduction of
nickel(I) or a sulfonyl anion. Finally, 8 is reduced in the presence of a proton and affords β-
hydroxysulfones 2. Then, the produced sulfonyl radical 5 reacts with alkenes or is converted to
sulfonyl anion 4 by nickel(I). Consequently, the catalytic process does not require a large excess
of sodium sulfinates and phosphine as a reductant.
Scheme 3. Hydroxysulfonylation of styrene in the absence of oxygen
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4-MeC6H4SO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
NH4PF6
OH
SO2C6H4Me-4
Ph
Ph
DMF, AcOH, H2O, 60 °C
under N2, 18 h
trace
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Scheme 4. A reaction in the presence of TEMPO
4-MeC6H4SO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
NH4PF6, TEMPO (1 equiv.)
OH
SO2C6H4Me-4
Ph
Ph
DMF, AcOH, H2O, 60 °C
air, 18 h
Not observed
Scheme 5. A reaction in the absence of H2O
4-MeC6H4SO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
NH4PF6
OH
O
SO2C6H4Me-4
SO2C6H4Me-4
+
Ph
Ph
Ph
DMF, AcOH, 60 °C,
56%
12%
air, 18 h
18
Scheme 6. A reaction in the presence of H2 O
4-MeC6H4SO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
NH4PF6
18OH
SO2C6H4Me-4
Ph
Ph
DMF, AcOH, H218O,
Not obseved
60 °C, air, 18 h
Figure 1. A plausible reaction mechanism
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H2O
O2, H+
NiILn
NiIILn
NiIILn
Ar2SO2Na
NiILn
4
7
8
9
2
•
or NiIILn
•
Ar SO2
Ar2SO2
OH
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SO2Ar2
+ H2O
5
Ar1
5
2
Ar1
1
or NiILn
2
H+
Ar SO2Na
O2
SO2Ar2
Ar1
SO2Ar2
•
Ar1
8
6
•
NiIILn or Ar2SO2
•
O2
O2
SO2Ar2
Ar1
NiILn or Ar2SO2Na
7
Attention was next focused on the selective synthesis of β-ketosulfones. As a first target, the
reaction of styrene with sodium 4-toluenesulfinate under oxygen atmosphere was evaluated.
Unfortunately, the expected oxosulfonylation did not ultimately proceed; the corresponding β-
hydroxysulfone was produced in 50% yield (Scheme 7).
On the contrary, when alkynes were employed, a reaction of phenyl acetylene and 1-phenyl 1-
propyne gave the expected β-ketosulfone in 60% and 41% yields, respectively (Scheme 8).
Scheme 7. A reaction under oxygen atomsphere
4-MeC6H4SO2Na,
NiBr2-TEEDA (1:1, 5 mol%)
OH
O
NH4PF6
SO2PhMe-4
SO2PhMe-4
Ph
+
Ph
Ph
DMF, AcOH, H2O, 60 °C
under O2, 18 h
50 %
trace
Scheme 8. Ketosulfonylation of alkynes
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4-MeC6H4SO2Na,
NiBr2-bpy (1:1, 5 mol%)
O
R
Ph
R
Ph
AcOH, H2O, 60 °C, air
18 h
1
SO2C6H4Me-4
3
9
R = H: 60% (3a)
R = Me: 41% (3o)
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In conclusion, nickel-catalyzed hydroxysulfonylation of alkenes was achieved using sodium
sulfinates in air. The procedure enabled the selective synthesis of β-hydroxysulfones in good
yields. Furthermore, the method enabled oxosulfonylation of alkynes with sodium sulfinates,
affording β-ketosulfones.
Experimental Section
1
13
General Procedure and Chemicals. All reactions were carried out in air. H and C NMR
spectra were recorded at 270 and 67.5 MHz, respectively. Chemical shifts are reported in δ ppm
1
referenced to an internal tetramethylsilane standard for H NMR and chloroform-d (δ 77.0) for
13C NMR. Compounds 2a5a, 2f5a, 2i5a, 2j5a, 2k5a, 2n5a, 2o5a, 2p5a, 3a8 and 3o8 showed the
identical spectra reported in the literature.
Typical procedure for nickel-catalyzed hydroxysulfonylation of alkenes: Synthesis of 2-
phenyl-1-(4-methylphenylsulfonyl)-ethane-2-ol (2a) (Table 2, entry 1)
To a mixture of styrene (31.2 mg, 0.3 mmol), sodium 4-toluenesulfinate (58.8 mg, 0.33 mmol),
and NH4PF6 (14.7 mg, 0.09 mmol), in DMF (0.3 mL), AcOH (0.1 mL) and H2O (0.2 mL) were
added NiBr2 (3.2 mg, 0.015 mmol) and (Et2NCH2)2 (2.6 mg, 0.015 mmol), and the mixture was
stirred at 60 °C for 18 h in air. After the residue was dissolved in Et2O, the solution was washed
with H2O and saturated sodium chloride and dried over anhydrous magnesium sulfate.
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Chromatography on silica gel (60% diethyl ether / hexane) gave 2-phenyl-1-(4-
methylphenylsulfonyl)-ethane-2-ol 2a (72.8 mg, 88%): white solid. mp: 68.5−69.5 °C; 1H NMR
(270 MHz, CDCl3) δ 7.83 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 8.2 Hz, 2H), 7.31−7.26 (m, 5H), 5.24
(d, J = 9.9 Hz, 1H), 3.72 (brs, 1H), 3.47 (dd, J = 14.5 and 9.9 Hz, 1H), 3.31 (dd, J = 14.5 and 1.3
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Hz, 1H), 2.46 (s, 3H); C{1H} NMR (67.5 MHz, CDCl3) δ 145.2, 140.7, 136.1, 130.1, 128.7,
128.3, 127.9, 125.6, 68.4, 63.9, 21.6; IR (CHCl3) 3615, 1620, 1445, 1302, 1172 cm-1; Anal.
Calcd for C15H16O3S: C, 65.19; H, 5.84. Found: C, 65.10; H, 5.86.
2-Phenyl-1-(4-methylphenylsulfonyl)-ethane-2-ol (2b): The title compound was obtained as
1
colorless liquid (70.0 mg, 80%). H NMR (270 MHz, CDCl3) δ 7.88 (d, J = 8.9 Hz, 2H),
7.33−7.26 (m, 5H), 7.03 (d, J = 8.9 Hz, 2H), 5.24 (d, J = 9.6 Hz, 1H), 3.89 (s, 3H), 3.76 (brs, 1H),
3.47 (dd, J = 14.5 and 9.6 Hz, 1H), 3.31 (dd, J = 14.5 and 2.0 Hz, 1H); 13C{1H} NMR (67.5
MHz, CDCl3) δ 164.0, 140.7, 130.2, 129.3, 128.7, 128.3, 125.6, 114.6, 68.5, 64.2, 55.7; IR
(CHCl3) 3507, 1596, 1497, 1296, 1137 cm-1; Anal. Calcd for C15H16O4S: C, 61.62; H, 5.52.
Found: C, 61.80; H, 5.37.
2-Phenyl-1-(4-chlorophenylsulfonyl)-ethane-2-ol (2c): The title compound was obtained as a
white solid (62.1 mg, 70%). mp: 103.5 −105.0 °C. 1H NMR (270 MHz, CDCl3) δ 7.87 (d, J = 8.9
Hz, 2H), 7.53 (d, J = 8.9 Hz, 2H), 7.31−7.26 (m, 5H), 5.27 (d, J = 9.7 Hz, 1H), 3.51 (dd, J = 14.5
and 9.7 Hz, 1H), 3.49 (brs, 1H), 3.33 (dd, J = 14.5 and 2.0 Hz, 1H); C{1H} NMR (67.5 MHz,
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CDCl3) δ 140.8, 140.5, 137.8, 129.7, 129.5, 128.8, 128.4, 125.6, 68.5, 63.9; IR (CHCl3) 3517,
1582, 1477, 1313, 1149 cm-1; Anal. Calcd for C14H13ClO3S: C, 56.66; H, 4.42. Found: C, 56.87;
H, 4.38.
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2-Phenyl-1-(4-fluorophenylsulfonyl)-ethane-2-ol (2d): The title compound was obtained as
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colorless liquid (63.8 mg, 76%). H NMR (270 MHz, CDCl3) δ 7.99−7.94 (m, 2H), 7.35−7.21
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(m, 7H), 5.28 (d, J = 9.8 Hz, 1H), 3.51 (dd, J = 14.1 and 9.8 Hz, 1H), 3.49 (brs, 1H), 3.34 (dd, J
= 14.1 and 2.0 Hz, 1H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 165.9 (d, 1J(C, F) = 256.9 Hz), 140.6,
135.3 (d, 4J(C, F) = 3.4 Hz), 131.0 (d, 3J(C, F) = 9.5 Hz), 128.8, 128.4, 125.6, 116.7 (d, 2J(C, F) = 21.0
Hz), 68.6, 64.1; IR (CHCl3) 3501, 1592, 1494, 1290, 1139 cm-1; Anal. Calcd for C14H13FO3S: C,
59.99; H, 4.67. Found: C, 60.27; H, 4.76.
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2-Phenyl-1-phenylsulfonyl-ethane-2-ol (2e): The title compound was obtained as a white solid
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(59.0 mg, 75%). mp: 90.0−91.5 °C. H NMR (270 MHz, CDCl3) δ 7.96 (d, J = 8.2 Hz, 2H),
7.72−7.56 (m, 3H), 7.33−7.26 (m, 5H), 5.29 (dd, J = 9.0 and 2.0 Hz, 1H), 3.67 (d, J = 2.0 Hz,
1H), 3.51 (dd, J = 14.2 and 9.0 Hz, 1H), 3.34 (dd, J = 14.2 and 2.0 Hz, 1H); 13C{1H} NMR (67.5
MHz, CDCl3) δ 140.6, 139.2, 134.1, 129.5, 128.8, 128.3, 127.9, 125.6, 68.4, 63.9; IR (CHCl3)
3619, 1621, 1447, 1307, 1147 cm-1; Anal. Calcd for C14H14O3S: C, 64.10; H, 5.38. Found: C,
64.20; H, 5.32.
2-(4-Methylphenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2f): The title compound was
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obtained as colorless liquid (61.1 mg, 70%).; H NMR (270 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz,
2H), 7.37 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.3 Hz, 2H), 7.11 (d, J = 8.3 Hz, 2H), 5.20 (d, J = 9.7
Hz, 1H), 3.66 (brs, 1H), 3.47 (dd, J = 14.2 and 9.7 Hz, 1H), 3.29 (dd, J = 14.2 and 2.0 Hz, 1H),
2.46 (s, 3H), 2.30 (s, 3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 145.1, 138.1, 137.7, 136.2, 130.0,
129.3, 127.9, 125.6, 68.3, 63.9, 21.6, 21.0; IR (CHCl3) 3502, 1597, 1515, 1313, 1133 cm-1; Anal.
Calcd for C16H18O3S: C, 66.18; H, 6.25. Found: C, 65.91; H, 6.31.
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2-(4-Methoxyphenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2g): The title compound was
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obtained as colorless liquid (65.3 mg, 71%). H NMR (270 MHz, CDCl3) δ 7.82 (d, J = 8.4 Hz,
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2H), 7.37 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 8.9 Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 5.19 (d, J = 9.9
and 1.8 Hz, 1H), 3.77 (s, 3H), 3.66 (brs, 1H), 3.47 (dd, J = 14.2 and 9.9 Hz, 1H), 3.29 (dd, J =
14.2 and 1.8 Hz, 1H), 2.46 (s, 3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 159.5, 145.1, 136.2,
132.9, 130.0, 127.9, 126.9, 114.6, 68.1, 63.9, 55.2, 21.6; IR (CHCl3) 3506, 1598, 1514, 1302,
1137 cm-1; Anal. Calcd for C16H18O4S: C, 62.72; H, 5.92. Found: C, 62.92; H, 5.95.
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2-(4-Acetoxyphenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2h): The title compound was
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obtained as a white solid (61.8 mg, 68%). mp: 102.7−104.0 °C. H NMR (270 MHz, CDCl3) δ
7.84 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 7.05 (d, J = 8.1 Hz,
2H), 5.26 (d, J = 10.4 Hz, 1H), 3.76 (brs, 1H), 3.45 (dd, J = 14.2 and 10.4 Hz, 1H), 3.30 (dd, J =
14.2 and 1.6 Hz, 1H), 2.47 (s, 3H), 2.28 (s, 3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 169.4,
150.4, 145.4, 138.2, 136.0, 130.1, 127.9, 126.8, 121.9, 68.0, 63.9, 21.7, 21.1; IR (CHCl3) 3514,
1754, 1598, 1289, 1137 cm-1; Anal. Calcd for C17H18O5S: C, 61.06; H, 5.43. Found: C, 60.96; H,
5.41.
2-(4-Chlorophenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2i): The title compound was
obtained as a white solid (57.3 mg, 62%). mp: 88.0−91.0 °C. 1H NMR (270 MHz, CDCl3) δ 7.82
(d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.30−7.21 (m, 4H), 5.23 (d, J = 9.6 Hz, 1H), 3.81 (d,
J = 2.0 Hz, 1H), 3.43 (dd, J = 14.2 and 9.6 Hz, 1H), 3.28 (dd, J = 14.4 and 2.0 Hz, 1H), 2.47 (s,
3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 145.4, 139.1, 135.9, 134.0, 130.1, 128.9, 127.9, 127.0,
67.8, 63.8, 21.7; IR (CHCl3) 3513, 1598, 1493, 1303, 1137 cm-1; Anal. Calcd for C15H15ClO3S:
C, 57.97; H, 4.86. Found: C, 57.86; H, 4.80.
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2-(4-Fluorophenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2j): The title compound was
obtained as a white solid (57.3 mg, 65%). mp: 91.5−92.1 °C. 1H NMR (270 MHz, CDCl3) δ 7.83
(d, J = 8.3 Hz, 2H,), 7.39 (d, J = 8.3 Hz, 2H), 7.30−7.25 (m, 2H), 7.03−6.97 (m, 2H), 5.25 (d, J =
9.0 Hz, 1H), 3.81 (brs, 1H), 3.45 (dd, J = 14.5 and 9.0 Hz, 1H), 3.29 (dd, J = 14.5 and 2.0 Hz,
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1H), 2.47 (s, 3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ 162.4 (d, J(C, F) = 245.0 Hz), 145.4,
136.4 (d, 4J(C, F) = 3.4 Hz), 135.9, 130.1, 128.0, 127.4 (d, 3J(C, F) = 8.1 Hz), 115.6 (d, 2J(C, F) = 21.6
Hz), 67.8, 63.9 (d, 5J(C, F) = 1.3 Hz), 21.7; IR (CHCl3) 3512, 1599, 1511, 1302, 1136 cm-1; Anal.
Calcd for C15H15FO3S: C, 61.21; H, 5.14. Found: C, 61.33; H, 5.12.
2-(2-Methoxyphenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2k): The title compound was
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obtained as a white solid (57.0 mg, 65%). mp: 116.1-118.0 °C. H NMR (270 MHz, CDCl3) δ
7.85 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 7.2 Hz, 1H), 7.39 (d, J = 8.2 Hz, 2H), 7.25−7.14 (m, 2H),
7.08 (d, J = 7.2 Hz, 1H), 5.43 (d, J = 9.7 Hz, 1H), 3.68 (brs, 1H), 3.40 (dd, J = 14.5 and 9.7 Hz,
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1H), 3.23 (dd, J = 14.5 and 1.6 Hz, 1H), 2.47 (s, 3H), 2.09 (s, 3H); C{1H} NMR (67.5 MHz,
CDCl3) δ 145.3, 138.7, 136.0, 133.7, 130.5, 130.1, 128.0, 127.9, 126.6, 125.3, 65.0, 62.9, 21.7,
18.5; IR (CHCl3) 3515, 1598, 1460, 1312, 1139 cm-1; Anal. Calcd for C16H18O3S: C, 66.18; H,
6.25. Found: C, 66.23; H, 6.26.
2-(2-Bromophenyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2l): The title compound was
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obtained as a white solid (65.7 mg, 74%). mp: 105.0−106.0 °C. H NMR (270 MHz, CDCl3) δ
7.90 (d, J = 8.6 Hz, 2H), 7.66 (d, J = 7.8 and 1.6 Hz, 1H), 7.44−7.32 (m, 4H), 7.13 (td, J = 7.8
and 1.6 Hz, 1H), 5.36 (d, J = 10.0 Hz, 1H), 4.05 (d, J = 1.6 Hz, 1H), 3.52 (dd, J = 14.5 and 1.3
Hz, 1H), 3.23 (dd, J = 14.5 and 10.0 Hz, 1H), 2.47 (s, 3H); 13C{1H} NMR (67.5 MHz, CDCl3) δ
145.4, 139.3, 135.4, 132.6, 130.1, 129.6, 128.3, 128.0, 127.5, 120.8, 67.6, 61.8, 21.7; IR (CHCl3)
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3515, 1598, 1447, 1300, 1140 cm-1; Anal. Calcd for C15H15BrO3S: C, 50.71; H, 4.26. Found: C,
50.37; H, 4.17.
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2-(2-Naphtyl)-1-(4-methylphenylsulfonyl)-ethane-2-ol (2m): The title compound was obtained
as a white solid (60.7 mg, 62%). mp: 61.0−62.0 °C. 1H NMR (270 MHz, CDCl3) δ 7.86−7.77 (m,
6H), 7.48−7.45 (m, 2H), 7.37−7.33 (m, 3H), 5.42 (d, J = 9.6 Hz, 1H), 3.83 (d, J = 1.8 Hz, 1H),
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3.55 (dd, J = 14.3 and 9.6 Hz, 1H), 3.40 (dd, J = 14.3 and 1.8 Hz, 1H), 2.45 (s, 3H); C{1H}
NMR (67.5 MHz, CDCl3) δ 145.3, 137.9, 136.1, 133.2, 133.1, 130.1, 128.7, 128.0, 127.9, 127.7,
126.4, 126.3, 124.8, 123.3, 68.6, 63.9, 21.7; IR (CHCl3) 3512, 1598, 1404, 1313, 1135 cm-1;
Anal. Calcd for C19H18O3S: C, 69.91; H, 5.56. Found: C, 69.53; H, 5.52.
2-Phenyl-1-(4-methylphenylsulfonyl)-propan-2-ol (2n): The title compound was obtained as a
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white solid (61.0 mg, 73%). mp: 80.0−81.5 °C. H NMR (270 MHz, CDCl3) δ 7.49 (d, J = 8.2
Hz, 2H), 7.31−7.26 (m, 2H), 7.20−7.15 (m, 5H), 4.62 (brs, 1H), 3.70 (dd, J = 14.5 Hz, 1H), 3.58
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(dd, J = 14.5 Hz, 1H), 2.38 (s, 3H), 1.70 (s, 3H); C{1H} NMR (67.5 MHz, CDCl3) δ 144.5,
144.4, 137.3, 129.7, 128.2, 127.5, 127.1, 124.6, 73.1, 66.6, 30.7, 21.5; IR (CHCl3) 3506, 1598,
1495, 1312, 1157 cm-1; Anal. Calcd for C16H18O3S: C, 66.18; H, 6.25. Found: C, 66.07; H, 6.20.
(1R*, 2S*)-1-Phenyl-2-(4-methylphenylsulfonyl)-propan-2-ol (2o): The title compound was
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obtained as colorless liquid (65.7 mg, 75%). H NMR (270 MHz, CDCl3) δ 7.84 (d, J = 8.0 Hz,
2H), 7.44 (d, J = 8.0 Hz, 2H), 7.34−7.24 (m, 5H), 5.50 (brs, 1H), 3.33 (brs, 1H), 3.19 (dd, J = 7.2
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and 1.3 Hz, 1H), 2.47 (s, 3H), 1.19 (d, J = 7.2 Hz, 3H); C{1H} NMR (67.5 MHz, CDCl3) δ
145.2, 139.9, 134.3, 130.0, 128.7, 128.4, 127.6, 125.5, 69.2, 65.6, 21.6, 5.7; IR (CHCl3) 2526,
1597, 1452, 1301, 1143 cm-1; Anal. Calcd for C16H18O3S: C, 66.18; H, 6.25. Found: C, 66.43; H,
6.25.
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trans-2-(4-Methylphenylsulfonyl)tetralin-1-ol (2p): The title compound was obtained as a
white solid (60.9 mg, 67%). mp: 120.7−122.5 °C. 1H NMR (270 MHz, CDCl3) δ 7.84 (d, J = 7.9
Hz, 2H), 7.60 (d, J = 7.5 Hz, 1H), 7.40 (d, J = 7.9 Hz, 2H), 7.27−7.14 (m, 2H), 7.02 (d, J = 7.2
Hz, 1H), 5.21 (d, J = 9.2 Hz, 1H), 4.19 (d, J = 2.0 Hz, 1H), 3.42−3.33 (m, 1H), 2.82−2.76 (m,
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2H), 2.46 (s, 3H), 2.18−2.12 (m, 1H), 1.80−1.71 (m, 1H); C{1H} NMR (67.5 MHz, CDCl3) δ
145.5, 135.8, 134.8, 133.4, 129.9, 129.2, 127.9, 127.6, 127.6, 126.8, 67.5, 66.9, 27.9, 22.9, 21.6;
IR (CHCl3) 3523, 1598, 1493, 1290, 1141 cm-1; Anal. Calcd for C17H18O3S: C, 67.52; H, 6.00.
Found: C, 67.17; H, 6.07.
trans-2-(4-Methylphenylsulfonyl)-1H-inden-1-ol (2q): The title compound was obtained as a
white solid (51.1 mg, 59%). mp: 135.0−136.3 °C. 1H NMR (270 MHz, CDCl3) δ 7.86 (d, J = 8.2
Hz, 2H), 7.40-7.36 (m, 3H), 7.29−7.22 (m, 2H), 7.15−7.12 (m, 1H), 5.75 (d, J = 6.6 Hz, 1H),
3.88−3.79 (m, 1H), 3.27 (dd, J = 16.0 and 8.9 Hz, 1H), 3.11 (dd, J = 16.0 and 8.9 Hz, 1H), 2.95
(brs, 1H), 2.46 (s, 3H); C{1H} NMR (67.5 MHz, CDCl3) δ 145.2, 141.2, 137.7, 135.2, 130.1,
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128.9, 128.5, 127.7, 124.5, 124.4, 75.5, 72.9, 31.7, 21.7; IR (CHCl3) 3616, 1598, 1423, 1286,
1146 cm-1; Anal. Calcd for C16H16O3S: C, 66.64; H, 5.59. Found: C, 66.24; H, 5.52.
Typical procedure for nickel-catalyzed oxysulfonylation of alkynes: Synthesis of 1-phenyl-
2-(4-methylphenylsulfonyl)ethanone (3a) (Scheme 6)
To a mixture of 1-phenylacetyrene (32.9 mg, 0.3 mmol), sodium 4-toluenesulfinate (58.8 mg,
0.33 mmol), and NH4PF6 (14.7 mg, 0.09 mmol), in AcOH (0.15 mL) and H2O (0.15 mL) were
added NiBr2 (3.2 mg, 0.015 mmol) and bpy (2.3 mg, 0.015 mmol), and the mixture was stirred at
60 °C for 18 h in air using balloon. After the residue was dissolved in Et2O, the solution was
washed with H2O and saturated sodium chloride and dried over anhydrous magnesium sulfate.
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Chromatography on silica gel (50% diethyl ether / hexane) gave 1-phenyl-2-(4-
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methylphenylsulfonyl)ethanone 3a (49.2 mg, 60%): white solid. mp: 100.1−102.0 °C. H NMR
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(270 MHz, CDCl3) δ 7.95 (d, J = 7.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H),
7.48 (t, J = 7.2Hz, 2H), 7.33 (d, J = 8.6 Hz, 2H), 4.71 (s, 2H), 2.44 (s, 3H); 13C{1H} NMR (67.5
MHz, CDCl3) δ 188.1, 145.4, 135.7, 135.7, 134.3, 129.8, 129.3, 128.8, 128.6, 63.6, 21.7; IR
(CHCl3) 1681, 1598, 1327, 1155 cm-1; Anal. Calcd for C15H14O3S: C, 65.67; H, 5.14. Found: C,
65.76; H, 5.16.
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1-Phenyl-2-(4-methylphenylsulfonyl)propanone (3o): The title compound was obtained as a
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white solid (35.4 mg, 41%). mp: 85.9−87.0 °C; H NMR (270 MHz, CDCl3) δ 7.98 (d, J = 7.2
Hz, 2H), 7.66 (d, J = 8.2 Hz, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.48 (t, J = 7.2Hz, 2H), 7.31 (d, J =
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8.2 Hz, 2H), 5.15 (q, J = 6.9 Hz, 1H), 2.43 (s, 3H), 1.55 (dd, J = 6.9 Hz, 3H); C{1H} NMR
(67.5 MHz, CDCl3) δ 192.5, 145.3, 136.2, 134.0, 132.9, 129.0, 129.5, 129.2, 128.7, 64.9, 21.7,
13.2; IR (CHCl3) 1682, 1597, 1449, 1326, 1149 cm-1; Anal. Calcd for C16H16O3S: C, 66.64; H,
5.59. Found: C, 66.30; H, 5.62.
1
Supporting Information. Copies of the H NMR and 13C NMR Spectra are provided. This
material is available free of charge via the Internet at http://pubs.acs.org.
References
1 Selected reviews: (a) Metzner, P.; Thuillier, A. Sulfur Reagents in Organic Synthesis;
Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W. Eds.; Academic Press: San Diego, 1994. (b)
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Paulmier, C. In Selenium Reagents and Intermediates in Organic Synthesis; Baldwin, J. E. Ed.;
Organic Chemistry Series 4; Pergamon Press Ltd.: Oxford, 1986. (c) Wirth, T. Ed.
Organoselenium Chemistry; Topics in Current Chemistry 208; Springer-Verlag; Heidelberg;
2000. (d) Ley, S. V.; Thomas, A. W. Angew. Chem. Int. Ed. 2003, 42, 5400–5449. (e) Kondo, T.;
Mitsudo, T. Chem. Rev. 2000, 100, 3205–3220. (f) Beletskaya, I. P.; Ananikov, V. P. Chem. Rev.
2011, 111, 1596–1636. (g) Partyka, D. V. Chem. Rev. 2011, 111, 1529–1595. (h) Allen, S. E.;
Walvoord, R. R.; Padilla-Salinas, R.; Kozlowski, M. C. Chem. Rev. 2013, 113, 6234−6458. (i)
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Lee, C.; Liu, C.; Badsara, S. S. Chem. Asian J. 2014, 9, 706−722. (j) Shen, C.; Zhang, P.; Sun,
Q.; Bai, S.; Andy Hor, T. S.; Liu, X. Chem. Soc. Rev. 2015, 44, 291−314.
2 (a) Uemura, S. Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon
Press Ltd.: New York, 1991, Vol. 7, Chapter 6.2. (b) Backväll, J.-E.; Ericsson, A. J. Org. Chem.
1994, 59, 5850−5851.
3 Selected paper of sulfonylations: (a) Wang, S.-F.; Chuang, C.-P.; Lee, J.-H.; Liu, S.-T.
Tetrahedron 1999, 55, 2273−2288. (b) Riggi, J. De, Surzur, J.-M.; Bertrand, M. P. Tetrahedron
1990, 46, 5285−5294. (c) Fang, J.-M.; Chen, M.-Y. Tetrahedron Lett. 1987, 28, 2853−2856. (d)
Back, T. G.; Krishna, M. V. J. Org. Chem. 1987, 52, 4265−4269. (e) Wei, W.; Liu, X.; Yang, D.;
Dong, R,; Cui, Y.; Yuan, F.; Wang, H. Tetrahedron Lett. 2015, 56, 1808−1811.
4 Selected paper of metal-mediated sulfonylations: (a) Truce, W. E.; Goralski, C. T. J. Org.
Chem. 1971, 36, 2536−2538. (b) Sinnreich, J.; Asscher, M. J. Chem. Soc., Perkin Trans. I 1972,
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(d) Beaulieu, C.; Guay, D.; Wang, Z.; Evans, D. A. Tetrahedron Lett. 2004, 45, 3233−3236. (e)
Kar, A.; Sayyed, Iliyas, A.; Lo Wei, F.; Kaiser Hanns, M.; Tse, M. K. Org. Lett. 2007, 9,
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(c) Taniguchi, N. Tetrahedron 2014, 70, 1984−1990.
8 Oxosulfonylation of alkynes: Handa, S.; Fennewald, J. C.; Lipshutz, B. H. Angew. Chem. Int.
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9 Selected review: (a) Smadja, W. Synlett 1993, 1−26. (b) Porter, N. D.; Giese, B.; Curran, D. P.
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