Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism

Article abstract of DOI:10.1002/ejoc.201900097

Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.

Full text of DOI:10.1002/ejoc.201900097

DOI: 10.1002/ejoc.201900097
Full Paper
Sulfinate Synthesis
Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited:
Improved Synthesis and Revised Reaction Mechanism
Yuan-Zhao Ji,[a] Hui-Jing Li,*[a] Jin-Yu Zhang,[a] and Yan-Chao Wu*[a,b]
Abstract: Reaction of alcohols with sodium arenesulfinates proved sulfinate synthesis. The improved sulfinate synthetic
could afford either sulfones or sulfinates, and O-attack of sulf- protocol possesses many advantages such as a high sulfinate/
inate anions onto the in situ generated carbocation intermedi- sulfone selectivity, a broad substrate scope, metal-free, and mild
ates from alcohols was the previous proposed reaction mecha- reaction conditions. The revised reaction mechanism necessi-
nism in many syntheses of sulfinates. This concept, which is tates revision of many previous proposed reaction mechanisms
often used consciously or unconsciously, was revised herein by in literatures.
using isotopic labeling experiments and development of an im-
Introduction
8a–c, not sulfones 3a–c, based on the NMR spectroscopic data
and spectra reported by Sreedhar (Scheme 1d).[5] Considering
the importance of sulfinates in the field of chemistry, biology
Alcohols are highly attractive starting materials in organic syn-
thesis as they are abundant, inexpensive, and often readily
available.[1] Since hydroxyl group is a poor leaving group, sub-
stitution of an alcohol usually consists of transformation of the
hydroxyl group to a better leaving group such as a halide and
a sulfonate, and subsequently substitution of the resulting alco-
hol derivative with an appropriate nucleophile.[2] For instance,
substitution of alcohol derivatives, mainly alkyl halides 1, with
sodium arenesulfinates 2 has been extensively investigated for
the preparation of sulfones 3 (Scheme 1a).[3] Although an ar-
enesulfinate anion (4 or 5) is a gemini nucleophile, the sulfur
acts as the attack atom in the most cases because of its higher
nucleophilicity compared to the one of oxygen.[4] Inspiringly,
Sreedhar reported a direct sulfonylation of alcohols 7 with
sodium arenesulfinates 2 using iron chloride (FeCl3) and tri-
methylsilyl chloride (TMSCl) as promoters, in which S-attack of
arenesulfinate anions 5 onto the in situ generated carbocations
6 was the proposed reaction mechanism (Scheme 1b).[5] Xiong
reported a direct sulfination of alcohols 7 with sodium sulf-
inates 2 promoted by boron trifluoride etherate (BF3·Et2O), in
which O-attack of sulfinate anions 4 onto the carbocations 6
was the proposed reaction pathway (Scheme 1c).[6] Actually, re-
action of primary benzyl alcohols 7a–c with sodium arenesulf-
inate 2a under Sreedhar's procedure[5] also afforded sulfinates
[a] School of Marine Science and Technology
Harbin Institute of Technology
2 Wenhuaxi Road, Weihai 264209, P.R. China
E-mail: lihuijing@iccas.ac.cn
http://homepage.hit.edu.cn/pages/lihuijing
[b] Beijing National Laboratory for Molecular Sciences (BNLMS)
Institute of Chemistry Chinese Academy of Sciences
No.2, 1st North Street, Zhongguancun, Beijing 100190, P.R. China
E-mail: ycwu@iccas.ac.cn
http://homepage.hit.edu.cn/pages/wuyanchao
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201900097.
Scheme 1. Selected synthetic protocols for the synthesis of sulfones or sulf-
inates.
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and pharmaceutical sciences,[7,8] this inspiring result triggered this reaction, but no better results were obtained in comparison
us to optimize the reaction conditions for the synthesis of sulf- to that with the use of TMSCl as the promoter (entries 4–7). The
inates.
solvent played an important role in this reaction. The reaction
did not work with the use of DMF, THF or 1,4-dioxane as the
solvent (entries 8–10). With the use of DCE, toluene, CH3CN,
CH3NO2 and DMSO in comparison to CH2Cl2, lower yields were
observed (entries 7 and 11–15). The molar ratio of 7a to 2a was
also important for this reaction, and increasing yields of sulf-
inate 8a were observed with the use of appropriate amounts
of excess benzyl alcohol (7a, entries 4 and 16–17). The yield of
sulfinate 8a was further increased to 83 % when the molar ratio
of 7a to 2a was increased from 1 to 2 (entries 16–18). No further
increase was observed when the molar ratio of 7a to 2a ex-
ceeded 2 (entries 16–19). Parameter optimization identified the
most effective loading of TMSCl as the 2.0 equivalents of so-
dium p-toluenesulfinate (2a, entries 18 and 20–23). A slight
lower yield of sulfinate 8a was observed when the reaction was
performed under reflux (45 °C) in comparison to that at room
temperature (25 °C, entries 22 and 24). The choice of reaction
Results and Discussion
Reaction of benzyl alcohol (7a) with sodium p-toluenesulfinate
(2a) was used as a probe for evaluating the reaction conditions,
and the representative results are summarized in Table 1.
Following Sreedhar's procedure [FeCl3 (15 mol-%), TMSCl
(1.2 equiv.), CH2Cl2, 45 °C],[5] the treatment of benzyl alcohol
(7a, 1.0 equiv.) and sodium p-toluenesulfinate (2a, 1.2 equiv.)
afforded sulfinate 8a in 43 % yield within 3 h (Table 1, entry 1).
The yield of sulfinate 8a was increased from 43 % to 55 % by
treating benzyl alcohol (7a) with a slight excess of sodium p-
toluenesulfinate (2a) under otherwise identical conditions (en-
tries 1 and 2). The reaction went equally well at room tempera-
ture (25 °C, entries 2 and 3). A higher yield of sulfinate 8a was
observed when the reaction was performed in the absence of
FeCl3 (entries 3 and 4). A series of other silicon reagents such time was also found to be of importance to improve this reac-
as TIPSCl, TBDMSCl and DMSCl were further investigated for tion efficiency, and the complete consumption of sodium p-
Table 1. Optimization of the reaction conditions.[a]
Entry
Promoter
Solvent
Temp.
Yield [b]
1[c]
2
3
4
5
6
7
8
9
10
11
12
13
14
15
FeCl3, TMSCl
FeCl3, TMSCl
FeCl3, TMSCl
TMSCl
TIPSCl
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
DMF
45 °C
45 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
25 °C
45 °C
25 °C
25 °C
25 °C
25 °C
43 %
55 %
55 %
67 %
0
44 %
65 %
0
TBDMSCl
DMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
–
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
TMSCl
THF
1,4-dioxane
DCE
0
0
51 %
55 %
12 %
26 %
trace
61 %
75 %
83 %
83 %
0
87 %
93 %
93 %
91 %
85 %
94 %
93 %
93 %
toluene
CH3CN
CH3NO2
DMSO
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
16[d]
17[e]
18[f]
19[g]
20[f]
21[f,h]
22[f,i]
23[f,j]
24[f,i]
25[f,i,k]
26[f,i,l]
27[f,i,m]
28[f,i,l,n]
[a] General conditions: 7a (0.6 mmol), 2a (0.5 mmol), silicon reagent (0.6 mmol) with/without FeCl3 (15 mol-%) in solvent (2.0 mL) at 25 °C for 3 h. [b] Isolated
yields. [c] 0.5 mmol of 7a and 0.6 mmol of 2a. [d] 0.5 mmol of 7a. [e] 0.8 mmol of 7a. [f] 1.0 mmol of 7a. [g] 1.2 mmol of 7a. [h] 0.8 mmol of TMSCl. [i]
1.0 mmol of TMSCl. [j] 1.2 mmol of TMSCl. [k] 0.5 h. [l] 1.0 h. [m] 1.5 h. [n] Reaction was carried out at 1.07 g scale of 2a (6.0 mmol). TMS = trimethylsilyl.
TIPS = triisopropylsilyl. TBDMS = tert-butyldimethylsilyl. DMS = dimethylsilyl. DCE = 1,2-dichloroethane. DMSO = dimethyl sulfoxide. DMF = N,N-dimethylform-
amide. THF = tetrahydrofuran. Temp. = temperature.
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toluenesulfinate (2a) cannot guarantee to yield the highest
yield of sulfinate 8a. Parameter optimization based on this con-
sideration identified 1 h as the most appropriate reaction time
(entries 22 and 25–27). Indeed, treatment of benzyl alcohol (7a)
and sodium p-toluenesulfinate (2a) under the optimized reac-
tion conditions for 1 h afforded sulfinate 8a in 94 % yield (en-
tries 26). Furthermore, scaling up sodium p-toluenesulfinate
(2a) to 1.07 g (6.0 mmol) the reaction provided the yield at an
excellent level (Table 1, entry 28).
Table 2. TMSCl-promoted sulfinate synthesis from benzyl alcohols 7 and
sodium p-toluenesulfinate (2a).[a]
The optimized reaction conditions proved to be effective for
a wide range of benzyl alcohols, and the representative results
are listed in Table 2. With the aromatic ring bearing hydrogen
atoms, electron-donating and electron-withdrawing groups,
benzyl alcohols 7a–k reacted smoothly with sodium p-toluene-
sulfinate (2a) in the presence of TMSCl (2 equiv.) in CH2Cl2 at
25 °C to afford sulfinates 8a–k in 63–94 % yields within 1 h
(Table 2, entries 1–11). A decreasing yield was observed with
the use of a 2-substituted benzyl alcohol (7d or 7j) in compari-
son to a 4-substituted benzyl alcohol (7c or 7i) as the substrate,
indicating that the steric factor of benzyl alcohols 7 affects the
reaction (Table 2, entries 3 and 4, 9 and 10). The treatment of
4-methoxybenzyl alcohol (7l) with sodium p-toluenesulfinate
(2a) gave a sulfone product in FeCl3/TMSCl system, whereas it
provided exclusively sulfinate 8l under our conditions, albeit at
a lower reaction temperature (Table 2, entry 12). Reaction of
1-phenylethanol (7m) with 2a under the same conditions gave
sulfinate 8m as a sole product (90 % yield, Table 2, entries 12
and 13). However, this reaction in either the FeCl3/TMSCl or
BF3·Et2O system yielded exclusively a sulfone product based on
its NMR spectroscopic data reported by Sreedhar[5] and Xiong.[6]
The result indicated that our sulfinate method expanded the
substrate scope of alcohols.
Sulfination of alkyl and allyl alcohols with sodium p-toluene-
sulfinate (2a) were subsequently investigated (Table 3). Simple
primary/secondary alkyl alcohols, such as methanol (7n), eth-
anol (7o) and isopropanol (7p), reacted smoothly with 2a. un-
der the standard conditions to give sulfinates 8n–p in 90–91 %
yields (Table 3, entries 1–3). tert-Butanol, a sterically hindered
alkyl alcohol, reacted uneventfully with 2a under the standard
conditions to afford sulfinate 8q in 50 % yield (entry 4). Phen-
ethyl alcohol (7r) has also been investigated, which reacted
with 2a under the standard conditions to give sulfinate 8r in
92 % yield (entry 5). Cyclic alcohols, including cyclopentanol
(7s), 2,3-dihydro-1H-inden-2-ol (7t) and cyclohexanol (7u), re-
acted with 2a under the standard conditions to afford exclu-
sively sulfinates 8s–u in 75–82 % yields (Table 3, entries 6–8).
Instead, the reaction of 7u with 2a under Sreedhar's procedure
gave a sulfone as the sole product.[5] Our sulfinate synthesis
and Sreedhar sulfone synthesis could complement each other
to enrich the reaction diversity. Cinnamyl alcohol (7v) and
methallyl alcohol (7w), two allyl alcohols, reacted with 2a suc-
cessfully to afford sulfinates 8v–w in 75 % and 82 % yields, re-
spectively (Table 3, entries 9–10). These reactions are extremely
easy to perform without the need for using anhydrous solvent
and inert atmosphere and under mild reaction conditions.
[a] General conditions: 7 (1.0 mmol), 2a (0.5 mmol) and TMSCl (1.0 mmol) in
CH2Cl2 (2.0 mL) at 25 °C for 1 h. [b] Isolated yields. [c] The reaction was
performed at 0 °C.
(Table 4). The treatment of sodium benzenesulfinate (2b) with
benzyl alcohol (7a), ethanol (7o), phenethyl alcohol (7r) and
2,3-dihydro-1H-inden-2-ol (7t) under the standard conditions
The feasibility of this sulfinate synthesis was also checked afforded sulfinates 8x–aa in 64–77 % yields (Table 4, entries 1–
by using a serial of sodium arenesulfinates 2 as the substrates 4). Sodium 4-fluorobenzenesulfinate (2c) reacted smoothly with
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Table 3. TMSCl-promoted sulfinate synthesis from alkyl/allyl alcohols 7 and
sodium p-toluenesulfinate (2a).[a]
1-sulfinate (2k) was also investigated and it reacted smoothly
with ethanol (7o) under the standard conditions to afford
Table 4. TMSCl-promoted sulfinate synthesis from sodium arenesulfinates 2
and alcohols 7.[a]
[a] General conditions: 7 (1.0 mmol), 2a (0.5 mmol) and TMSCl (1.0 mmol) in
CH2Cl2 (2.0 mL) at 25 °C for 1 h. [b] Isolated yields. [c] The reaction was
performed at 0 °C.
benzyl alcohol (7a) and ethanol (7o) under the standard condi-
tions to generate sulfinates 8ab–ac in 80 % and 81 % yields,
respectively (entries 5 and 6). Sodium 4-chlorobenzenesulfinate
(2d) reacted equally well with benzyl alcohol (7a) and phen-
ethyl alcohol (7r) under the standard conditions to give sulf-
inates 8ad–ae in 84 % and 86 % yields, respectively (entries 7
and 8). By treatment of Sodium 4-bromobenzenesulfinate (2e)
with ethanol (7o) in the presence of TMSCl (2 equiv.) in CH2Cl2
at room temperature (25 °C) for 1 h, sulfinate 8af was isolated
in 83 % yield (entry 9). The treatment of benzyl alcohol (7a)
with sodium 4-methoxybenzenesulfinate (2f), sodium 4-nitro-
benzenesulfinate (2g), sodium 3-bromobenzenesulfinate (2h)
sodium 2-chlorobenzenesulfinate (2i) and sodium thiophene-2-
sulfinate (2j) under the standard conditions afforded sulfinates
8ag–ak in 70–95 % yields (entries 10–14). Sodium naphthalene-
[a] General conditions: 7 (1.0 mmol), 2a (0.5 mmol) and TMSCl (1.0 mmol) in
CH2Cl2 (2.0 mL) at 25 °C for 1 h. [b] Isolated yields.
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sulfinate 8aj in 82 % yield (Table 4, entry 15). This sulfinate that the previous proposed reaction mechanism involving O-
synthetic protocol offers attractive industrial prospects in the attack of a sulfinate anion onto an in situ generated carbocation
view point of metal-free, high selectivity, and facile reaction intermediate (Scheme 1c) might be not right in most cases.
conditions.
The reaction mechanism of sodium arenesulfinates-involved
sulfinate synthesis was next studied. Usually, nucleophilic sub-
stitution of alcohol derivatives 1 with sodium arenesulfinates 2
affords sulfones 3 instead of sulfinates 8 (Scheme 1a).[3] Al-
though this concept may be not always valid due to the differ-
ent reaction conditions, the chemoselectivity of this nucleo-
philic substitution reaction is quite clear.[3] The sulfur of an
arenesulfinate anion (4 or 5) has a higher nucleophilicity than
the one of oxygen, and thus acts as the attacking atom
(Scheme 1a).[4,9] Direct reaction of alcohols 7 with sodium
arenesulfinates 2 could afford either sulfones 3 or sulfinates 8
(Scheme 1b and Scheme 1c).[5,6] Interestingly, the sulfinate/sulf-
one selectivity was found to be related to the reactivity of alco-
hols 7. Treatment of primary benzyl alcohol 7a with sodium
arenesulfinate 2a under Sreedhar'[5] or Xiong's[6] reaction condi-
tions gave exclusively sulfinate 8a. In contrast, sulfone 3m
(Scheme 2) instead of sulfinate 8m was obtained as the sole
product when secondary benzyl alcohol 7m, a relatively more
activated alcohol compared to primary benzyl alcohol 7a, was
used as the substrate under otherwise identical conditions.[5,6]
To understand this unexpected result, a serial of control experi-
ments were performed and the representative results were illus-
trated in Scheme 2. When sulfinate 8a was subjected to Sreed-
har'[5] or Xiong's[6] reaction conditions, no reaction took place
Scheme 2. Verification experiments. I) our procedure (25 °C for equation a,
and the starting material was recovered (Scheme 2a). Instead,
sulfinate 8m under Sreedhar' or Xiong's reaction conditions was
e–f, 0 °C for Equation b–d). II) Sreedhar's procedure.[5] III) Xiong's procedure.[6]
converted to sulfone 3m in 40 % and 45 % yields, respectively
However, the concept that one oxygen atom of an arenesulf-
inate anion 4 acting as the nucleophilic attacking atom is often
used consciously or unconsciously to explain the formation of
sulfinates 8 (Scheme 1c), in which the arenesulfinate anion 4
was generated in situ from various reagents.[6,7c,7e,7i,11] Our work
necessitates revision of these previous proposed reaction mech-
anisms in literatures.
Based on the above results and related reports in the litera-
ture, a possible reaction mechanism is illustrated in Scheme 3.
Silyllation of sodium arenesulfinates 2 with TMSCl formed com-
pounds 9, which were converted to intermediates 10 by chelat-
ing with TMSCl. Nucleophilic substitution reaction of 10 with
alcohols 7 generated intermediates 11. Finally, detachment of
TMSCl from 11 afforded sulfinates 8 (Scheme 3).
(Scheme 2b). As in the case of sulfinate 8m, sulfinates 8l and
8v under Sreedhar' or Xiong's reaction conditions were con-
verted to sulfones 3m and 3v, respectively (Scheme 2c and
Scheme 2d). The results supported that reaction of benzyl alco-
hol 7a with sodium arenesulfinate 2a under Sreedhar' or
Xiong's reaction conditions could afford sulfinate 8a, whereas
sulfones 3l, 3m and 3v were obtained with the use of relatively
more activated alcohols 7l, 7m and 7v as the substrates under
otherwise identical conditions. In contrast to Sreedhar' and
Xiong's synthetic procedures,[5,6] our sulfinate synthesis were
carried out under milder conditions (TMSCl, 25 °C or 0 °C),
which tolerated more sulfinates and thus expanded the sub-
strate scope of substrates (Scheme 2a–d). Treatment of L-men-
thol (7x) with sodium arenesulfinate 2a under the reaction con-
ditions of our sulfinate synthesis afforded sulfinate 8am in 85 %
yield in a 1:1 diastereomeric ratio (Scheme 2e),[10] similar to the
result reported by Oliveira,[7f] indicating that the in situ genera-
tion of a carbocation intermediate (Scheme 1c) from alcohol 7l
maybe not a major pathway for this reaction. In order to get
more information, reaction of 18O-labelled benzyl alcohol (7y)
and sodium p-toluenesulfinate (2a) was performed in the pres-
ence of TMSCl in CH2Cl2 at room temperature (25 °C), which
afforded sulfinate 8an in 90 % yield within 1 h (Scheme 2f).
When this reaction was carried out following Sreedhar'[5] and
Xiong's[6] procedures, sulfinate 8an was obtained in 42 % and
78 % yields, respectively (Scheme 2f). These results indicated
Scheme 3. Proposed mechanism.
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132.4, 129.6, 129.2, 128.6, 125.3, 65.6, 21.4, 21.1; FTIR (film): 2923,
1596, 1518, 1453, 1134, 1081, 908, 852, 811, 767, 732 cm–1; HRMS
(ESI) m/z: Calcd for C15H16NaO2S [M + Na]+: 283.0763, found
Conclusions
We have developed an improved sulfinate synthesis via the tan-
dem reaction of alcohols and sodium arenesulfinates in the 283.0768.
presence of trimethylsilyl chloride. The synthetic protocol offers
4-Nitrobenzyl 4-methylbenzenesulfinate (8c): White solid; m.p. =
38–39 °C; 106.2 mg, 73 % yield; 1H NMR (400 MHz, CDCl3) δ: 8.15
(d, J = 7.8 Hz, 2H), 7.62 (d, J = 7.1 Hz, 2H), 7.42 (d, J = 7.7 Hz, 2H),
7.35 (d, J = 7.3 Hz, 2H), 5.07 (d, J = 12.6 Hz, 1H), 4.59 (d, J = 12.6 Hz,
1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 147.6, 143.3, 143.0,
140.9, 129.8, 128.6, 125.2, 123.6, 63.3, 21.5; FTIR (film): 2925, 2855,
1522, 1346, 1135, 1081, 852, 814, 736 cm–1; HRMS (ESI) m/z: Calcd
for C14H14NO4S [M + H]+: 292.0638, found 292.0640.
attractive industrial prospects as the reaction took place at
room/zero temperature without the need for using transition
metal catalysts and inert atmosphere, and displayed a high
sulfinate/sulfone selectivity and a broad substrate scope. Impor-
tantly, the reaction mechanism of many sulfinate syntheses
from alcohols and sodium arenesulfinates was revised by using
isotopic labeling experiments and development of an improved
sulfinate synthesis. The result will put the related mechanistic
consideration for arenesulfinate anions-involved sulfinate for-
mation back on the right track.
2-Nitrobenzyl 4-methylbenzenesulfinate (8d): Yellow oil;
91.7 mg, 63 % yield; 1H NMR (400 MHz, CDCl3) δ: 8.04 (d, J = 8.1 Hz,
1H), 7.70–7.60 (m, 4H), 7.45 (t, J = 7.3 Hz, 1H), 5.43 (d, J = 14.5 Hz,
1H), 5.02 (d, J = 14.5 Hz, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ: 147.2, 143.3, 141.1, 133.7, 132.4, 129.8, 129.5, 128.7, 125.1, 124.8,
62.5, 21.5; FTIR (film): 2925, 2856, 1525, 1342, 1134, 1081, 813,
729 cm–1; HRMS (ESI) m/z: Calcd for C14H13NNaO4S [M + Na]+:
314.0457, found 314.0452.
Experimental Section
General Experimental Methods: Common reagents and materials
were purchased from commercial sources and were used without
further purification. Organic extracts were, in general, dried with
anhydrous sodium sulfate (Na2SO4). TLC plates were visualized by
exposure to ultra violet light (UV). IR spectra were recorded by using
an Electrothemal Nicolet 380 spectrometer. High-resolution mass
spectra (HRMS) were recorded by using an Electrothemal LTQ-Orbi-
trap mass spectrometer. Melting points were measured by using
a Gongyi X-5 microscopy digital melting point apparatus and are
uncorrected. 1H NMR and 13C NMR spectra were obtained by using
a Bruker Avance III 400 MHz NMR spectrometer. Chemical shifts for
protons are reported in parts per million (δ scale) and are refer-
enced to residual protium in the NMR solvents [CDCl3: δ 7.26].
Chemical shifts for carbon resonances are reported in parts per mil-
lion (δ scale) and are referenced to the carbon resonances of the
solvent (CDCl3: δ 77.0). Data are represented as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet,
m = multiplet, br = broad), integration, and coupling constant in
Hertz (Hz).
4-(Trifluoromethyl)benzyl 4-methylbenzenesulfinate (8e): Yel-
low foam, 135.1 mg, 86 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.63
(d, J = 7.9 Hz, 2H), 7.57 (d, J = 7.9 Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H),
7.35 (d, J = 8.2 Hz, 2H), 5.05 (d, J = 12.1 Hz, 1H), 4.58 (d, J = 12.1 Hz,
1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 143.2, 141.2, 139.7,
130.4 (q, JC-F = 32.5 Hz, 1C), 129.8, 128.4, 125.4 (q, JC-F = 3.7 Hz, 1C),
125.3, 64.1, 21.4; FTIR (film): 1613, 1579, 1429, 1308, 1134, 1082,
1036, 881, 859, 814, 790, 674 cm–1; HRMS (ESI) m/z: Calcd for
C15H13F3NaO2S [M + Na]+: 337.0481, found 337.0479.
3,5-Difluorobenzyl 4-methylbenzenesulfinate (8f): Colorless oil;
112.8 mg, 80 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.62 (d, J = 7.9 Hz,
2H), 7.35 (d, J = 7.9 Hz, 2H), 6.78–6.69 (m, 3H), 4.94 (d, J = 12.2 Hz,
1H), 4.48 (d, J = 12.3 Hz, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ:162.9 (dd, JC-F = 249.2, 12.7 Hz, 1C), 143.3, 141.1, 139.6 (t, JC-F
=
9.29 Hz, 1C), 129.8, 125.2, 110.8 (dd, JC-F = 18.7, 7.1 Hz, 1C), 103.6
(t, JC-F = 25.2 Hz, 1C), 63.5, 21.4; FTIR (film): 1629, 1599, 1464, 1368,
1323, 1137, 1119, 946, 854, 813, 759, 673 cm–1; HRMS (ESI) m/z:
Calcd for C14H12F2NaO2S [M + Na]+: 305.0418, found 305.0421.
General Experimental Procedure for the synthesis of Sulfinates:
The mixture of an alcohol (1.0 mmol), a sodium arylsulfinate
(0.5 mmol) and TMSCl (1 mmol) in CH2Cl2 (3.0 mL) was stirred at
25 °C for 1 h, then water (5 mL) and dichloromethane (10 mL) were
added. The two layers were separated, and the aqueous phase was
extracted with dichloromethane (3 × 10 mL). The combined organic
extracts were washed by brine, dried with anhydrous Na2SO4, fil-
tered, and concentrated. The residue was purified by flash chroma-
tography on silica gel (100–200 mesh) to afford the desired sulfinate
8a–8an.
4-Chlorobenzyl 4-methylbenzenesulfinate (8g): Colorless oil;
120.4 mg, 86 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.64 (d, J = 7.6 Hz,
2H), 7.36 (d, J = 7.7 Hz, 2H), 7.30 (d, J = 7.7 Hz, 2H), 7.21 (d, J =
7.7 Hz, 2H), 4.99 (d, J = 11.6 Hz, 1H), 4.52 (d, J = 11.6 Hz, 1H), 2.45
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 143.0, 141.4, 134.2, 134.1, 129.8,
129.7, 128.6, 125.2, 64.5, 21.4; FTIR (film): 2923, 2852, 1596, 1476,
1446, 1365, 1140, 1081, 1057, 919, 870, 812, 767, 747, 696 cm–1
;
HRMS (ESI) m/z: Calcd for C14H13ClNaO2S [M + Na]+: 303.0217, found
303.0221.
3,4-Dichlorobenzyl 4-methylbenzenesulfinate (8h): Yellow oil;
133.4 mg, 85 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.60 (d, J = 7.6 Hz,
2H), 7.37–7.32 (m, 3H), 7.28 (s, 1 H), 4.91 (d, J = 11.9 Hz, 1H), 4.46
(d, J = 12.0 Hz, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 143.2,
141.1, 135.8, 132.5, 132.3, 130.4, 130.2, 129.8, 127.5, 125.2, 63.3, 21.5;
FTIR (film): 2925, 2852, 1596, 1473, 1400, 1360, 1133, 1081, 1033,
Benzyl 4-methylbenzenesulfinate (8a): Pale yellow oil, 115.6 mg,
94 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.67 (d, J = 7.9 Hz, 2H),
7.38–7.29 (m, 7H), 5.06 (d, J = 11.4 Hz, 1H), 4.58 (d, J = 11.4 Hz, 1H),
2.45 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 142.8, 141.5, 135.4, 129.7,
128.5, 128.4, 125.2, 65.5, 21.4; FTIR (film): 3408, 3031, 2922, 2850,
2537, 1596, 1454, 1131, 1104, 1080, 1036, 904, 812, 764, 695 cm–1
;
873, 813, 757, 710, 662 cm–1
; HRMS (ESI) m/z: Calcd for
HRMS (ESI) m/z: Calcd for C14H14NaO2S [M + Na]+: 269.0607, found
C14H12Cl2NaO2S [M + Na]+: 336.9827, found 336.9831.
269.0604.
4-Bromobenzyl 4-methylbenzenesulfinate (8i): Colorless oil;
134.4 mg, 83 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.61 (d, J = 8.1 Hz,
2H), 7.43 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.13 (d, J =
4-Methylbenzyl 4-methylbenzenesulfinate (8b): Yellow oil,
120.9 mg, 93 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.63 (d, J = 7.6 Hz,
2H), 7.34 (d, J = 7.5 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.3 Hz, 2H), 4.95 (d, J = 11.7 Hz, 1H), 4.48 (d, J = 11.7 Hz, 1H), 2.42
8.4 Hz, 2H), 5.00 (d, J = 11.1 Hz, 1H), 4.53 (d, J = 11.1 Hz, 1H), 2.43
(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 143.0, 141.3, 134.6, 131.6, 130.0,
129.7, 125.2, 122.4, 64.5, 21.4; FTIR (film): 2923, 1595, 1490, 1234,
(s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 142.7, 141.6, 138.3,
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1134, 1070, 1014, 920, 847, 802, 733 cm–1; HRMS (ESI) m/z: Calcd 637 cm–1; HRMS (ESI) m/z: Calcd for C10H14NaO2S [M + Na]+:
for C14H13BrNaO2S [M + Na]+: 346.9712, found 346.9709.
221.0607, found 221.0610.
tert-Butyl 4-methylbenzenesulfinate (8q): Colorless oil; 53.0 mg,
50 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.55 (d, J = 7.7 Hz, 2H), 7.30
(d, J = 7.7 Hz, 2H), 2.40 (s, 3H), 1.54 (s, 9H); 13C NMR (100 MHz,
CDCl3) δ: 143.6, 141.9, 129.5, 124.7, 82.5, 29.8, 21.3; FTIR (film):
3411, 2923, 2852, 1712, 1596, 1456, 1288, 1144, 1080, 812, 683,
655 cm–1; HRMS (ESI) m/z: Calcd for C11H16NaO2S [M + Na]+:
235.0763, found 235.0769.
2-Bromobenzyl 4-methylbenzenesulfinate (8j): Yellow oil;
126.7 mg, 78 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.69 (d, J = 7.6 Hz,
2H), 7.55 (d, J = 7.9 Hz, 1H), 7.40 (d, J = 7.6 Hz, 1H), 7.36 (d, J =
7.7 Hz, 2H), 7.31 (t, J = 7.9 Hz, 1H), 7.19 (t, J = 7.5 Hz, 1H), 5.15 (d,
J = 12.1 Hz, 1H), 4.74 (d, J = 12.1 Hz, 1H), 2.45 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 143.0, 141.4, 135.1, 132.7, 130.4, 129.9, 129.7,
127.5, 125.3, 123.4, 65.4, 21.5; FTIR (film): 2922, 1596, 1472,
1443, 1364, 1143, 1081, 1031, 919, 869, 812, 767, 744, 694, 658,
626 cm–1; HRMS (ESI) m/z: Calcd for C14H13BrNaO2S [M + Na]+:
346.9712, found 346.9714.
Phenethyl 4-methylbenzenesulfinate (8r): Colorless oil; 119.6 mg,
92 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 7.8 Hz, 2H),
7.33–7.23 (m, 5H), 7.18 (t, J = 7.1 Hz, 2H), 4.26 (dd, J = 16.5, 7.6 Hz,
1H), 3.84 (dd, J = 16.6, 7.5 Hz, 1H), 2.96 (t, J = 7.0 Hz, 2H), 2.44 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 142.5, 141.4, 137.2, 129.5, 128.8,
128.3, 126.5, 125.1, 64.6, 36.1, 21.4; FTIR (film): 2960, 2888, 1597,
1497, 1454, 1362, 1175, 1130, 1082, 1043, 1006, 990, 911, 867, 814,
734, 701 cm–1; HRMS (ESI) m/z: Calcd for C15H16NaO2S [M + Na]+:
283.0763, found 283.0769.
3-Phenoxybenzyl 4-methylbenzenesulfinate (8k): Colorless oil;
143.6 mg, 85 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.62 (d, J = 7.9 Hz,
2H), 7.37–7.27 (m, 5H), 7.33 (d, J = 8.0 Hz, 2H), 7.13 (t, J = 7.4 Hz,
1H), 7.03–6.92 (m, 5H), 4.99 (d, J = 11.6 Hz, 1H), 4.53 (d, J = 11.6 Hz,
1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 157.4, 156.8, 142.8,
141.4, 137.5, 129.8, 129.69, 129.68, 125.2, 123.4, 123.0, 119.0, 118.54,
118.45, 64.9, 21.4; FTIR (film): 2924, 2852, 1584, 1446, 1365, 1214,
1132, 1081, 926, 880, 815, 754, 691 cm–1; HRMS (ESI) m/z: Calcd for
C20H18NaO3S [M + Na]+: 361.0869, found 361.0873.
Cyclopentyl 4-methylbenzenesulfinate (8s): Pale yellow oil,
89.6 mg, 80 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.58 (d, J = 7.8 Hz,
2H), 7.31 (d, J = 7.8 Hz, 2H), 4.83–4.80 (m, 1H), 2.41 (s, 3H), 1.90–
1.87 (m, 2H), 1.72–1.49 (m, 6H); 13C NMR (100 MHz, CDCl3) δ: 142.8,
142.4, 129.6, 125.1, 80.7, 34.1, 33.7, 23.30, 23.28, 21.4; FTIR (film):
2960, 2872, 1597, 1493, 1451, 1355, 1167, 1133, 1080, 955, 933, 849,
812, 637, 627 cm–1; HRMS (ESI) m/z: Calcd for C12H16NaO2S [M +
Na]+: 247.0763, found 247.0776.
4-Methoxybenzyl 4-methylbenzenesulfinate (8l): The reaction
was performed at 0 °C. Colorless oil; 89.7 mg, 65 % yield; 1H NMR
(400 MHz, CDCl3) δ: 7.62 (d, J = 8.1 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H),
7.20 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 8.6 Hz, 2H), 4.97 (d, J = 11.1 Hz,
1H), 4.51 (d, J = 11.1 Hz, 1H), 3.79 (s, 3H), 2.43 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ: 159.7, 142.7, 141.6, 130.3, 129.6, 127.4, 125.3,
113.9, 65.5, 55.2, 21.4; FTIR (film): 2932, 2836, 1612, 1514, 1250,
1130, 1033, 907, 812, 792 cm–1; HRMS (ESI) m/z: Calcd for
C15H16NaO3S [M + Na]+: 299.0712, found 299.0717.
2,3-Dihydro-1H-inden-2-yl 4-methylbenzenesulfinate (8t): Pale
1
yellow oil, 102.0 mg, 75 % yield; H NMR (400 MHz, CDCl3) δ: 7.61
(d, J = 8.0 Hz, 2H), 7.36–7.16 (m, 6H), 5.19–5.14 (m, 1H), 3.37–2.98
(m, 4H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 142.6, 142.2,
139.8, 139.7, 129.6, 126.8, 125.3, 125.1, 124.49, 124.46, 77.8, 40.9,
40.4, 21.4; FTIR (film): 3024, 2923, 1596, 1483, 1460, 1420, 1358,
1211, 1178, 1131, 1081, 1035, 1003, 943, 855, 813, 742 cm–1; HRMS
(ESI) m/z: Calcd for C16H16NaO2S [M + Na]+: 295.0763, found
295.0775.
1-Phenylethyl 4-methylbenzenesulfinate (8m): The reaction was
performed at 0 °C. Yellow oil; 117.0 mg, 90 % yield; 1H NMR
(400 MHz, CDCl3) δ: 7.56 (d, J = 7.9 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H),
7.40–7.30 (m, 4H), 7.22–7.20 (m, 2H), 7.15–7.13 (m, 1H), 5.46 (dd, J =
13.0, 6.4 Hz, 0.5H), 5.37 (dd, J = 12.8, 6.4 Hz, 0.5 H), 2.41 (s, 1.6H),
2.38 (s, 1.4H), 1.71 (s, 3H), 1.67 (d, J = 6.5 Hz, 1.4H), 1.58 (d, J =
6.5 Hz, 1.6H); 13C NMR (100 MHz, CDCl3) δ: 142.6, 142.5, 142.4, 141.9,
141.6, 141.3, 129.5, 129.3, 128.5, 128.2, 128.1, 127.7, 126.3, 126.1,
125.2, 124.8, 75.3, 24.1, 23.9, 21.4, 21.3; FTIR (film): 3032, 2979, 2927,
1596, 1493, 1134, 872, 764, 697 cm–1; HRMS (ESI) m/z: Calcd for
C15H16NaO2S [M + Na]+: 283.0763, found 283.0768.
Cyclohexyl 4-methylbenzenesulfinate (8u): Yellow oil; 97.6 mg,
82 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.59 (d, J = 7.4 Hz, 2H), 7.30
(d, J = 7.6 Hz, 2H), 4.34–4.30 (m, 1H), 2.40 (s, 3H), 2.01–1.98 (m, 1H),
1.76–1.69 (m, 3H), 1.61–1.43 (m, 3H), 1.39–1.17 (m, 3H); 13C NMR
(100 MHz, CDCl3) δ: 142.8, 142.3, 129.5, 124.9, 77.6, 33.6, 33.5, 25.0,
23.79, 23.77, 21.4; FTIR (film): 2934, 2857, 1596, 1493, 1449, 1400,
1135, 1083, 941, 800, 7560, 638 cm–1; HRMS (ESI) m/z: Calcd for
C13H18NaO2S [M + Na]+: 261.0920 Found: 261.0924.
Methyl 4-methylbenzenesulfinate (8n): Colorless oil; 77.3 mg,
91 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.58 (d, J = 7.7 Hz, 2H), 7.33
(d, J = 7.7 Hz, 2H), 3.45 (s, 3H), 2.42 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 142.7, 140.9, 129.6, 125.3, 49.3, 21.4; FTIR (film): 2939,
1596, 1452, 1138, 1081, 963, 813, 682, 637 cm–1; HRMS (ESI) m/z:
Calcd for C8H10NaO2S [M + Na]+: 193.0294, found 193.0296.
Cinnamyl 4-methylbenzenesulfinate (8v): The reaction was per-
1
formed at 0 °C. Yellow oil; 102.2 mg, 75 % yield; H NMR (400 MHz,
CDCl3) δ: 7.67 (d, J = 7.7 Hz, 2H), 7.38–7.28 (m, 7H), 6.59 (d, J =
15.8 Hz, 1H), 6.21 (dt, J = 15.8, 6.5 Hz, 1H), 4.68 (dd, J = 12.0, 6.5 Hz,
1H), 4.33 (dd, J = 11.9, 6.6 Hz, 1H), 2.45 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 142.8, 141.6, 135.9, 134.8, 129.7, 128.5, 128.1, 126.6, 125.2,
123.2, 64.8, 21.4; FTIR (film): 2923, 2867, 1597, 1493, 1449, 1366,
1133, 1080, 967, 912, 837, 813, 754, 734, 693 cm–1; HRMS (ESI) m/z:
Calcd for C16H16NaO2S [M + Na]+: 295.0763, found 295.0766.
Ethyl 4-methylbenzenesulfinate (8o): Pale yellow oil, 82.8 mg,
90 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.59 (d, J = 7.6 Hz, 2H), 7.32
(d, J = 7.6 Hz, 2H), 4.12–4.04 (m, 1H), 3.75–3.67 (m, 1H), 2.41 (s, 3H),
1.26 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 142.6, 141.8,
129.6, 125.1, 60.7, 21.4, 15.5; FTIR (film): 2980, 2925, 2854, 1597,
1443, 1385, 1126, 1080, 1006, 883, 813, 710 cm–1; HRMS (ESI) m/z:
Calcd for C9H12NaO2S [M + Na]+: 207.0450, found 207.0464.
2-Methylallyl 4-methylbenzenesulfinate (8w): Colorless oil;
86.1 mg, 82 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.59 (d, J = 6.7 Hz,
2H), 7.32 (d, J = 7.1 Hz, 2H), 4.96 (s, 1H), 4.91 (s, 1H), 4.41 (d, J =
11.9 Hz, 1H), 3.97 (d, J = 11.9 Hz, 1H), 2.41 (s, 3H), 1.71 (s, 3H); 13C
NMR (100 MHz, CDCl3) δ: 142.7, 141.6, 139.8, 129.6, 125.1, 114.4,
67.7, 21.4, 19.3; FTIR (film): 2984, 2927, 2870, 1597, 1457, 1402, 1380,
Isopropyl 4-methylbenzenesulfinate (8p): Colorless oil; 89.1 mg,
90 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.58 (d, J = 7.8 Hz, 2H), 7.30
(d, J = 7.7 Hz, 2H), 4.62–4.53 (m, 1H), 2.40 (s, 3H), 1.36 (d, J = 6.2 Hz,
1H), 1.22 (d, J = 6.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ: 142.6, 1316, 1289, 1177, 1148, 1130, 1087, 914, 815, 734, 709, 683 cm–1
;
142.3, 129.5, 124.9, 72.5, 23.8, 23.6, 21.3; FTIR (film): 2977, 2924,
1597, 1452, 1384, 1373, 1142, 1103, 1083, 917, 841, 812, 743,
HRMS (ESI) m/z: Calcd for C11H14NaO2S [M + Na]+: 233.0607, found
233.0611.
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Benzyl benzenesulfinate (8x): Colorless oil, 94.7 mg, 77 % yield;
7.0 Hz, 1H), 2.93 (t, J = 6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ:
1H NMR (400 MHz, CDCl3) δ: 7.79–7.77 (m, 2H), 7.59–7.57 (m, 3H), 142.9, 138.3, 137.0, 129.1, 128.8, 128.4, 126.6, 65.2, 36.0; FTIR (film):
7.36–7.29 (m, 5H), 5.07 (d, J = 11.4 Hz, 1H), 4.60 (d, J = 11.4 Hz, 1H));
13C NMR (100 MHz, CDCl3) δ: 144.5, 135.4, 132.2, 129.1, 128.6, 128.5,
125.3, 65.9; FTIR (film): 3408, 3031, 2922, 2850, 2537, 1596, 1454,
1131, 1104, 1080, 1036, 904, 812, 764, 695 cm–1; HRMS (ESI) m/z:
Calcd for C13H12NaO2S [M + Na]+: 255.0450, found 255.0454.
2924, 2851, 1574, 1497, 1474, 1454, 1391, 1136, 1087, 1013, 963,
865, 827, 744, 699 cm–1; HRMS (ESI) m/z: Calcd for C14H13ClNaO2S
[M + Na]+: 303.0217, found 303.0225.
Ethyl 4-bromobenzenesulfinate (8af): Pale yellow oil; 103.3 mg,
83 % yield. 1H NMR (400 MHz, CDCl3): δ: 7.67 (d, J = 8.4 Hz, 2H),
7.57 (d, J = 8.4 Hz, 2H), 4.15–4.07 (m, 1H), 3.76–3.68 (m, 1H), 1.28
Ethyl benzenesulfinate (8y): Pale yellow oil, 63.8 mg, 75 % yield;
1H NMR (400 MHz, CDCl3) δ: 7.73–7.71 (m, 2H), 7.55–7.51 (m, 3H), (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ: 143.8, 132.2, 126.8,
4.16–4.08 (m, 1H), 3.77–3.69 (m, 1H), 1.28 (t, J = 7.1Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ: 144.7, 131.9, 128.9, 125.1, 60.9, 15.4; FTIR (film):
2982, 2928, 1475, 1444, 1385, 1328, 1133, 1097, 1081, 1067, 1004,
882, 755, 697 cm–1; HRMS (ESI) m/z: Calcd for C8H10NaO2S [M +
Na]+: 193.0294, found 193.0299.
126.8, 61.2, 15.5; FTIR (film): 2987, 2900, 1573, 1472, 1386, 1136,
1095, 1065, 1009, 882, 820, 728, 712 cm–1. HRMS (ESI) m/z: Calcd
for C8H9BrNaO2S [M + Na]+: 270.9399, found 270.9412.
Benzyl 4-methoxybenzenesulfinate (8ag): Pale yellow oil;
124.5 mg, 95 % yield. 1H NMR (400 MHz, CDCl3): δ: 7.67 (d, J =
8.8 Hz, 2H), 7.36–7.26 (m, 5H), 7.02 (d, J = 8.8 Hz, 2H), 5.01 (d, J =
11.4 Hz, 1H), 4.56 (d, J = 11.4 Hz, 1H), 3.85 (s, 3H); 13C NMR (100 MHz,
Phenethyl benzenesulfinate (8z): Pale yellow oil, 89.8 mg, 73 %
yield; 1H NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 7.1 Hz, 2H), 7.47–7.39
(m, 3H), 7.22–7.13 (m, 3H), 7.06 (d, J = 7.2 Hz, 2H), 4.17 (dt, J = 9.9, CDCl3): δ: 162.6, 135.9, 135.5, 128.4, 128.4, 128.3, 127.1, 114.3, 65.3,
7.2 Hz, 1H), 3.74 (dt, J = 9.9, 7.2 Hz, 1H), 2.86 (t, J = 7.2 Hz, 2H); 13C
55.4. FTIR (film): 2938, 1599, 1479, 1136, 1086, 1012, 923, 728 cm–1
.
NMR (100 MHz, CDCl3) δ: 144.5, 137.2, 132.0, 129.0, 128.9, 128.5, HRMS (ESI) m/z: Calcd for C14H14NaO3S [M + Na]+: 285.0556, found
126.6, 125.2, 65.0, 36.2; FTIR (film): 3028, 2924, 1497, 1454, 1444, 285.0549.
1373, 1132, 1081, 1066, 964, 908, 864, 750, 697 cm–1; HRMS (ESI)
Benzyl 4-nitrobenzenesulfinate (8ah): Pale yellow oil; 102.5 mg,
m/z: Calcd for C14H14NaO2S [M + Na]+: 269.0607, found 269.0619.
74 % yield. 1H NMR (400 MHz, CDCl3): δ: 8.37 (d, J = 8.6 Hz, 2H),
2,3-Dihydro-1H-inden-2-yl benzenesulfinate (8aa): Pale yellow
7.91 (d, J = 8.7 Hz, 2H), 7.37–7.34 (m, 3H), 7.29–7.26 (m, 2H), 5.10
oil, 83.8 mg, 64 % yield; H NMR (400 MHz, CDCl3) δ: 7.73–7.71 (m, (d, J = 11.4 Hz, 1H), 4.68 (d, J = 11.5 Hz, 1H); 13C NMR (100 MHz,
2H), 7.55–7.52 (m, 3H), 7.23–7.16 (m, 4H), 5.21–5.16 (m, 1H), 3.37– CDCl3): δ: 150.9, 150.0, 134.6, 128.8, 128.7, 128.6, 126.7, 124.2, 67.2.
3.20 (m, 2H), 3.10–2.98 (m, 2H); 13C NMR (100 MHz, CDCl3) δ: 145.2, FTIR (film): 2928, 2860, 1523, 1386, 1136, 1095, 1074, 1009, 823,
139.8, 139.7, 132.1, 129.0, 126.9, 125.2, 124.5, 78.2, 40.9, 40.5; FTIR
721 cm–1. HRMS (ESI) m/z: Calcd for C13H11NNaO4S [M + Na]+:
1
(film): 2919, 2849, 1481, 1461, 1444, 1419, 1356, 1313, 1210, 1189, 300.0301, found 300.0304.
1129, 1081, 1066, 1001, 939, 899, 852, 801, 736, 699 cm–1; HRMS
Benzyl 3-bromobenzenesulfinate (8ai): Pale yellow oil; 138.0 mg,
89 % yield. H NMR (400 MHz, CDCl3): δ: 7.91 (s, 1H), 7.71–7.67 (m,
2H), 7.43 (t, J = 7.8 Hz, 1H), 7.38–7.30 (m, 5H), 5.08 (d, J = 11.4 Hz,
1H), 4.64 (d, J = 11.4 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ: 146.6,
135.2, 134.9, 130.5, 128.6, 128.6, 128.5, 128.3, 123.9, 123.3, 66.2. FTIR
(ESI) m/z: Calcd for C15H14NaO2S [M + Na]+: 281.0607, found
1
281.0618.
Benzyl 4-fluorobenzenesulfinate (8ab): Colorless oil, 101.2 mg,
81 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.76–7.73 (m, 2H), 7.37–
7.33 (m, 3H), 7.28–7.26 (m, 2H), 7.22 (t, J = 8.5 Hz, 2H), 5.04 (d, J = (film): 2922, 1593, 1489, 1446, 1131, 1089, 1063, 883, 724 cm–1
.
11.4 Hz, 1H), 4.60 (d, J = 11.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ: HRMS (ESI) m/z: Calcd for C13H11BrNaO2S [M + Na]+: 332.9555, found
165.0 (d, JC-F = 253.2 Hz, 1C), 163.7, 140.4 (d, JC-F = 2.8 Hz, 1C),
135.1, 128.5, 128.5, 128.5, 127.8 (d, JC-F = 9.1 Hz, 1C), 116.3 (d, JC-
332.9559.
Benzyl 2-chlorobenzenesulfinate (8aj): Pale yellow oil; 113.1 mg,
85 % yield. 1H NMR (400 MHz, CDCl3): δ: 8.03–8.00 (m, 1H), 7.51–
7.46 (m, 2H), 7.43–7.40 (m, 1H), 7.36–7.28 (m, 5H), 5.10 (d, J =
11.3 Hz, 1H), 4.72 (d, J = 11.3 Hz, 1H); 13C NMR (100 MHz, CDCl3):
δ: 141.6, 135.0, 133.3, 132.6, 130.2, 128.5, 128.5, 128.4, 127.1, 126.4,
= 22.6 Hz, 1C), 66.0; FTIR (film): 3066, 2926, 1587, 1489, 1228,
F
1130, 1078, 934, 903, 836, 723, 693 cm–1; HRMS (ESI) m/z: Calcd for
C13H11FNaO2S [M + Na]+: 273.0356, found 273.0360.
Ethyl 4-fluorobenzenesulfinate (8ac): Pale yellow oil; 76.1 mg,
1
81 % yield. H NMR (400 MHz, CDCl3): δ = 7.72–7.17 (m, 4H), 4.13– 67.4. FTIR (film): 3374, 2976, 1577, 1475, 1392, 1084, 1044, 1002,
4.05 (m, 1H), 3.76–3.67 (m, 1H), 1.26 (t, J = 7.0 Hz, 3H); 13C NMR 834, 749 cm–1. HRMS (ESI) m/z: Calcd for C13H11ClNaO2S [M + Na]+:
(100 MHz, CDCl3): δ = 164.9 (d, JC-F = 251.1 Hz, 1C), 140.6 (d, JC-F
=
289.0060, found 289.0053.
3.1 Hz, 1C), 127.6 (d, JC-F = 9.1 Hz, 1C), 116.2 (d, JC-F = 22.3 Hz, 1C),
61.0, 15.5. FTIR (film): 2988, 2901, 1587, 1490, 1404, 1394, 11228,
1132, 1077, 1066, 1057, 1012, 880, 837, 813, 713, 668 cm–1. HRMS
(ESI) m/z: Calcd for C8H9FNaO2S [M + Na]+: 211.0199, found
211.0209.
Benzyl thiophene-2-sulfinate (8ak): Pale yellow oil; 83.3 mg, 70 %
yield. 1H NMR (400 MHz, CDCl3): δ: 7.67 (dd, J = 4.9, 1.1 Hz, 1H),
7.53 (dd, J = 3.7, 1.1 Hz, 1H), 7.38–7.30 (m, 5H), 7.17 (dd, J = 4.8,
3.8 Hz, 1H), 5.15 (d, J = 11.4 Hz, 1H), 4.75 (d, J = 11.4 Hz, 1H); 13C
NMR (100 MHz, CDCl3): δ: 147.6, 135.1, 131.6, 129.9, 128.6, 128.5,
127.7, 65.5. FTIR (film): 3177, 2955, 1513, 1444, 1332, 1035, 1009,
898, 735 cm–1. HRMS (ESI) m/z: Calcd for C11H10NaO2S2 [M + Na]+:
Benzyl 4-chlorobenzenesulfinate (8ad): Colorless oil, 111.7 mg,
84 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.70 (d, J = 8.2 Hz, 2H), 7.54
(d, J = 8.2 Hz, 2H), 7.37–7.36 (m, 3H), 7.30 (d, J = 7.7 Hz, 2H), 5.07 261.0014, found 261.0018.
(d, J = 11.4 Hz, 1H), 4.62 (d, J = 11.4 Hz, 1H); 13C NMR (100 MHz,
Ethyl naphthalene-1-sulfinate (8al): Pale yellow oil; 90.2 mg, 82 %
yield. H NMR (400 MHz, CDCl3): δ: 8.28 (d, J = 7.6 Hz, 2H), 7.16 (d,
CDCl3) δ: 143.1, 138.6, 135.1, 129.4, 128.6, 128.5, 126.82, 66.2; FTIR
(film): 3372, 1644, 1584, 1478, 1394, 1087, 1003, 824, 757, 647 cm–
1; HRMS (ESI) m/z: Calcd for C13H11ClNaO2S [M + Na]+: 289.0060,
found 269.0058.
1
J = 6.6 Hz, 2H), 8.00 (d, J = 7.6 Hz, 2H), 7.92 (d, J = 7.3 Hz, 2H), 7.60–
7.54 (m, 3H), 4.17–4.11 (m, 1H), 3.62–3.55 (m, 1H), 1.19 (t, J = 6.3 Hz,
3H). 13C NMR (100 MHz, CDCl3): δ: 139.1, 133.6, 132.7, 129.2, 128.7,
127.3, 126.6, 124.7, 124.2, 122.2, 60.5, 15.3. FTIR (film): 2980, 1505,
1441, 1383, 1345, 1262, 1191, 1144, 1125, 1096, 1004, 879, 801, 770,
738, 706, 667 cm–1. HRMS (ESI) m/z: Calcd for C12H12NaO2S [M +
Na]+: 243.0450, found 243.0469.
Phenethyl 4-chlorobenzenesulfinate (8ae): Pale yellow oil,
120.4 mg, 86 % yield; 1H NMR (400 MHz, CDCl3) δ: 7.51 (d, J = 8.4 Hz,
2H), 7.45 (d, J = 8.4 Hz, 2H), 7.50–7.41 (m, 4H), 7.30–7.20 (m, 3H),
7.14–7.12 (m, 2H), 4.24 (dt, J = 10.0, 6.9 Hz, 1H), 3.81 (dt, J = 9.9,
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(1R, 2S, 5R)-2-Isopropyl-5-methylcyclohexyl 4-methylbenzene-
sulfinate (8am): Yellow solid; m.p. = 105–106 °C; 125.2 mg, 85 %
1-Methyl-4-((1-phenylethyl)sulfonyl)benzene (3m): White solid;
m.p. = 130–131 °C; H NMR (400 MHz, CDCl3) δ: 7.44 (d, J = 8.2 Hz,
2H), 7.33–7.25 (m, 3H), 7.20 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 7.2 Hz,
1
1
yield; H NMR (400 MHz, CDCl3) δ: 7.59 (d, J = 7.5 Hz, 2H), 7.30 (d,
J = 7.2 Hz, 2H), 4.18 (td, J = 10.5, 3.6 Hz, 0.5H), 4.11 (td, J = 10.4, 2H), 4.24 (q, J = 7.2 Hz, 1H), 2.41 (s, 3H), 1.77 (d, J = 7.2 Hz, 3H); 13
C
3.5 Hz, 0.5H), 2.40 (s, 3H), 2.28–2.11 (m, 2H), 1.82–1.66 (m, 2H), 1.46–
NMR (100 MHz, CDCl3) δ: 144.3, 133.8, 129.3, 129.2, 129.1, 128.6,
1.17 (m, 4H), 1.07–0.70 (m, 11H); 13C NMR (100 MHz, CDCl3) δ: 143.2, 128.2, 65.9, 21.5, 14.0; FTIR (film): 2920, 2854, 1659, 1645, 1457,
143.0, 142.4, 142.3, 129.5, 124.8, 124.4, 81.9, 80.0, 48.1, 47.7, 43.5,
42.8, 33.9, 33.8, 31.7, 31.6, 29.6, 25.3, 25.1, 23.0, 22.9, 21.9, 21.8, 21.4,
20.7, 15.5, 15.3; FTIR (film): 2954, 2923, 2869, 1597, 1456, 1371, 1135,
956, 914, 851, 776, 757, 639 cm–1; HRMS (ESI) m/z: Calcd for
1373 cm–1; HRMS (ESI) m/z: Calcd for C15H16NaO2S [M + Na]+:
283.0763, found 283.0769.
1-(Cinnamylsulfonyl)-4-methylbenzene (3v): Yellow oil; 1H NMR
(400 MHz, CDCl3) δ: 7.75 (d, J = 8.2 Hz, 2H), 7.33–7.28 (m, 7H), 6.39
(d, J = 15.9 Hz, 1H), 6.10 (dt, J = 15.4, 7.6 Hz, 1H), 3.93 (d, J = 7.6 Hz,
2H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 138.9, 135.8,
135.5, 129.7, 128.6, 128.5, 128.4, 126.6, 115.3, 60.5, 21.6; FTIR (film):
2923, 2865, 1493, 1444, 1351, 1132, 1080, 813 cm–1; HRMS (ESI) m/z:
Calcd for C16H16NaO2S [M + Na]+: 295.0763, found 295.0766.
C
17H26NaO2S [M + Na]+: 317.1546, found 317.1549. The data match
with the literature.[7f]
(1R, 2S, 5R)-2-Isopropyl-5-methylcyclohexan-1-ol (7x) (CAS:
2216–51–5): The sulfinate 8ah (0.2 mmol) was hydrolyzed with ex-
cess 10 % aq. KOH in methanol (1 mL) at room temperature for
0.5 h, then water (5 mL) and EtOAc (10 mL) were added. The two
layers were separated, and the aqueous phase was extracted with
EtOAc (3 × 10 mL). The combined organic extracts were washed by
brine, dried with anhydrous Na2SO4, filtered, and concentrated to
Acknowledgments
This project was funded by the National Natural Science Foun-
dation of China (21672046 and 21372054), the Fundamental
Research Funds for the Central Universities (HIT.NSRIF.201701),
and the Innovation and Entrepreneurship Foundation from Hu-
ancui District of Wehai City.
1
give 93 % of menthol 7x. H NMR (400 MHz, CDCl3) δ: 3.39 (dt, J =
10.4, 4.3 Hz, 1H), 2.21–2.10 (m, 1H), 1.96–1.93 (m, 1H), 1.69–1.57 (m,
2H), 1.52 (s, 1H), 1.47–1.34 (m, 1H), 1.13–1.06 (m, 1H), 1.01–0.94 (m,
1H), 0.91 (d, J = 6.7 Hz, 3H), 0.90 (d, J = 6.2 Hz, 3H), 0.88–0.84 (m,
1H), 0.79 (d, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 71.4, 50.0,
44.9, 34.4, 31.5, 25.7, 23.0, 22.1, 20.9, 16.0; FTIR (film): 3234, 2953,
2926, 2869, 1462, 1446, 1044, 1025, 918, 669 cm–1; HRMS (ESI) m/z:
Calcd for C10H20NaO [M + Na]+: 179.1406, found 179.1409. The data
match with the literature.[10]
Keywords: Alcohols · Sodium arenesulfinates · Sulfinates ·
Isotopic labeling · Reaction mechanisms
General Experimental Procedure for the synthesis of Sulfones:
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Reaction conditions: I) The mixture of a sulfinate 8 (0.5 mmol) and
TMSCl (1 mmol) in CH2Cl2 (2.0 mL) was stirred at 0 °C for 1 h, then
water (5 mL) and dichloromethane (10 mL) were added. The two
layers were separated, and the aqueous phase was extracted with
dichloromethane (3 × 10 mL). The combined organic extracts were
washed by brine, dried with anhydrous Na2SO4, filtered, and con-
centrated. The residue was purified by flash chromatography on
silica gel (100–200 mesh) to afford the desired sulfones 3.
Reaction conditions: II) The mixture of a sulfinate 8 (0.5 mmol),
FeCl3 (0.075 mmol) and TMSCl (0.6 mmol) in CH2Cl2 (2.0 mL) was
stirred at 45 °C for 14 h, then water (5 mL) and dichloromethane
(10 mL) were added. The two layers were separated, and the aque-
ous phase was extracted with dichloromethane (3 × 10 mL). The
combined organic extracts were washed by brine, dried with anhy-
drous Na2SO4, filtered, and concentrated. The residue was purified
by flash chromatography on silica gel (100–200 mesh) to afford the
desired sulfones 3.
Reaction conditions: III) The mixture of a sulfinate 8 (0.5 mmol) and
BF3·Et2O (0.9 mmol) in CH2Cl2 (1.5 mL) was stirred at 50 °C for 3 h,
then water (5 mL) and dichloromethane (10 mL) were added. The
two layers were separated, and the aqueous phase was extracted
with dichloromethane (3 × 10 mL). The combined organic extracts
were washed by brine, dried with anhydrous Na2SO4, filtered, and
concentrated. The residue was purified by flash chromatography on
silica gel (100–200 mesh) to afford the desired sulfones 3.
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1-Methoxy-4-(tosylmethyl)benzene (3l): White solid; m.p. = 122–
123 °C; 1H NMR (400 MHz, CDCl3) δ: 7.50 (d, J = 8.2 Hz, 2H), 7.24 (d,
J = 8.1 Hz, 2H), 7.00 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 8.6 Hz, 2H), 4.22
(s, 2H), 3.78 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 159.9, 144.5, 131.9,
129.4, 128.6, 120.1, 113.9, 62.2, 55.2, 21.5; FTIR (film): 2924, 2851,
1597, 1474, 1291, 1136, 1089, 865 cm–1; HRMS (ESI) m/z: Calcd for
C15H16NaO3S [M + Na]+: 299.0712, found 299.0715.
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[10] In order to know the stereochemistry of the alcohol center, the sulfinate
8ah was subjected to hydrolysis to afford the L-menthol (7x). The spec-
troscopic data (1H and 13C NMR) of the 7x match with the reported
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Received: January 20, 2019
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Full Paper
Sulfinate Synthesis
Y.-Z. Ji, H.-J. Li,* J.-Y. Zhang,
Y.-C. Wu* ............................................ 1–11
Sodium
Arenesulfinates-Involved
Sulfinate Synthesis Revisited: Im-
proved Synthesis and Revised Reac-
tion Mechanism
Reaction of alcohols with sodium ar- anism in many syntheses of sulfinates.
enesulfinates could afford either sulf- This concept, which is often used con-
ones or sulfinates, and O-attack of sciously or unconsciously, was revised
sulfinate anions onto in situ generated herein by using isotopic labeling ex-
carbocation intermediates from alco- periments and development of an im-
hols was the previous proposed mech- proved sulfinate synthesis.
DOI: 10.1002/ejoc.201900097
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim