Sulfination of alcohols with sodium sulfinates promoted by BF3·OEt2: An unexpected access

Article abstract of DOI:10.1039/c5gc02846a

A BF₃·OEt₂-promoted direct substitution of various alcohols with sodium sulfinates affording sulfinates under mild conditions has been developed. Further reaction of the hydroxysteroids achieves the highly complex sulfinates in good yields, which are two potential pharmacophores routinely encountered in drug discovery.

Full text of DOI:10.1039/c5gc02846a

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Sulfination of alcohols with sodium sulfinates promoted by
BF3·OEt2: an unexpected access
Mingming Huang,a Liangzhen Hu,a Hang Shen,a Qing Liu,a Muhammad Ijaz Hussain,a Jing Pan,a and
Yan Xiong*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A BF3·OEt2-promoted direct substitution of various levels of a direct substitution of primary allylic amines with sodium
alcohols with sodium sulfinates affording sulfinates under mild sulfinate using boric acid to activate the NH2 group where the
conditions has been developed. Further elaboration of the NH2 group served as an effective leaving group to obtain stable
hydroxysteroids reaches the highly complex sulfinates in good allylic carbocation (eq. 2, Scheme 1).8 Sulfinate salts also
yields, two potential pharmacophores routinely encountered in served as the nucleophiles to attack the allylic carbon
drug discovery.
activated by palladium catalyst, and obtained allyl sulfones.
Inspired by these works about sodium sulfinate, we
summarized relevant mechanism9 and envisioned that S-attack
of sodium sulfinate onto the stable carbocation is capable of
generating the desired sulfones (toward left, Fig. 1).
Alcohols are one of the most common and versatile
compounds for natural products and key precursors for other
classes of chemicals in organic synthesis.1 Because of the lower
leaving ability of hydroxyl group in alcohols, nucleophilic
substitution of it is generally difficult.2 Requisite preactivation
of hydroxyl group to afford good leaving groups including
halide or mesylate were generally used previously.3 As a
subject of consistent interest for organic chemistry, our group
have demonstrated several direct substitutions of alcohols to
afford ethers, sulfonamides and diarylalkanes.4 In this context,
we wished to obtain sulfones by direct substitution of sodium
sulfinates utilizing the nucleophilicity of sulfur. Earlier
researches reported on the direct sulfonylation of alcohols
with sulfinic acids by using Brønsted acids including HCl, AcOH
and HCOOH to afford sulfones.5 An overview of previously
relevant works on the sulfonylation of alcohols to form sulfone
moiety could be produced by sodium sulfinate, sulfide, sulfinic
acid, sulfonyl chloride, potassium metabisulfite and
arenesulfonyl cyanides,6 of which sodium sulfinate is the most
favorable reagent, due to its superior stability and ease of
handling.
Scheme 1 Reported direct sulfonylation.
Continuous attractivity lies in a facile synthesis of sulfones
via a Baylis-Hillman adduct of p-toluenesulfonyl cyanide with
allylic alcohols in the presence of diisoproylethylamine was
reported by Reddy and Hu (eq. 1, Scheme 1).7 Tian developed
Fig. 1 Two ways for nucleophile of carbocation toward sulfone and
sulfinate.
a.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing
400030, China. E-mail: xiong@cqu.edu.cn
On the basis of our recent works, we assumed the initiation
of direct substitution of alcohols with sodium sulfinates by
means of boron trifluoride diethyl ether (BF3·OEt2) resulting in
carbocation. BF3·OEt2 is a special species: it serves as a
Brønsted acid in the presence of water and sometimes it acts
b.State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin
300071, China
† Footnotes relaꢀng to the ꢀtle and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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as Lewis acid due to its empty p-orbital. As a Brønsted acid, in oC gave rise to the product in the best NMR yield of 87% (82%
our former work, mixing BF3·OEt2 with H2O resulted in the for separation) (Table 1, entries 7-9). Moreover, it can be
formation of BF3-H2O which has promoted benzylation deduced that at 50 oC, less side reaction took place, by
reaction of arenes via a carbonium intermediate.4c,10 As a comparing the conversion with yield. Reaction times were
Lewis acid, it has been found a very efficient catalyst in a large investigated; as a result, increasing the reaction time from 4 h
amount of reactions. Our former studies have demonstrated to 8 h led to successively decreasing yields caused by
the BF3·OEt2 catalytic synthesis of bis(indolyl)methanes from increasing side reactions (Table 1, entries 10-12). Various
indoles and carbonyl compounds11 and etherification of strong polar and non-polar solvents were then screened,
alcohols4a, where catalyst loading can be lowered to 5‰ and subsequently, no desire products were detected in DMSO or
recoverable utilization was in high yield. Moreover, BF3·OEt2 THF (Table 1, entries 13 and 14), while 57% yield was obtained
participated cyanation of silyl enol ethers12 and direct N- in chloroform (Table 1, entry 15). With cyclohexane as solvent,
benzylation of sulfonamides with benzyl alcohols4b were also the 3a was afforded in yield of 41% (Table 1, entry 16). Upon
reported by our group. As an extension of these works, herein exposure to CH3NO2 or C2H5NO2, the lower activities were
we wish to report a direct sulfonylation of alcohols with observed with yields of 36% and 48%, respectively (Table 1,
sodium arenesulfinate.
entries 17 and 18).
To probe the feasibility of this hypothesis, we first
evaluated our investigations on the model reaction of benzyl
Table 1. Optimization of reaction conditionsa
alcohol
(1a) with sodium p-toulenesulfinate (2a) in the
o
presence of 20 mol% of BF3·OEt2 in dichloromethane at 45 C
for 3 h (Table 1, entry 1). As expected, the reaction took place.
When the product was analyzed based on NMR spectroscopy,
we found two peaks in doublet for benzyl hydrogen atoms
indicating different chemical environment (Fig. 2). It could be
preliminarily interpreted by the influence of chiral sulfur
center of the unexpected sulfinate 3a not the envisioned
sulfone. Through the structure of sulfinate 3a, it seemed that
3a
3a
4
T
t
Entry
χ
Solvent
Conv.b Yieldb
Yieldc
(%)
(oC.) (h)
(%)
15
30
42
69
83
82
66
88
90
88
89
95
0
(%)
15
26
41
68
80
73
63
87(82)d
81
74
70
69
0
1
0.2 CH2Cl2
1.0 CH2Cl2
1.4 CH2Cl2
1.6 CH2Cl2
1.8 CH2Cl2
2.0 CH2Cl2
1.8 CH2Cl2
1.8 CH2Cl2
1.8 CH2Cl2
1.8 CH2Cl2
1.8 CH2Cl2
1.8 CH2Cl2
1.8 DMSO
1.8 THF
45
45
45
45
45
45
35
50
55
50
50
50
50
50
50
50
3
3
3
3
3
3
3
3
3
4
5
8
3
3
3
3
3
3
< 1
9
2
3
11
14
12
19
15
5
sodium sulfinate was not converted to sulfinate anion I, and
4
only kept the form of sulfinic acid nucleophile II (see Figure 1).
During our manuscript preparation, we found a relevant
synthetic report firstly falling in same puzzles.13 Considering
the importance and bifunction of sulfinate anion in organic
synthesis,14 we kept going to accomplish this work (toward
right, Fig. 1).
5
6
7
8
9
10
13
19
34
0
10
11
12
13
14
15
16
17
18
0
0
0
1.8 CHCl3
1.8 CYH
67
93
66
63
57
41
36
48
11
< 1
< 1
10
1.8 CH3NO2 50
1.8 C2H5NO2 50
a Reaction conditions: 1a (0.5 mmol), 2a (0.65 mmol), BF3·OEt2
(specified), solvent (1.5 mL). The amount of 2a and the volume
of CH2Cl2 were optimized (for the details, see Table S1 in the
b
Supporting Information).
Determined by 1H NMR
Fig. 2 1H NMR doublet peaks for two benzyl hydrogen atoms of
spectroscopy using anisole as an internal standard on the basis
c
sulfinate.
1
of 1a
.
Determined by H NMR spectroscopy using anisole as
d Isolated yield.
an internal standard on the basis of 2a
.
We initially concentrated on the optimization of the
reaction conditions for the synthesis of sulfinate 3a. The
treatment of benzyl alcohol (1a) with 1.0-2.0 equivalents of
BF3·OEt2 yielded 26-80% of desired product 3a, accompanied
Table 2 Sulfination of different activated alcohols with sodium
p-toluenesulfinate salta
with 4-methylphenyl p-toluenesulfinate
4 (Table 1, entries 2-6),
and 1.8 equivalents of BF3·OEt2 was found to be the best. The
effect of different temperatures was studied; as a result, the
reaction was temperature-sensitive and the temperature of 50
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underwent the reaction smoothly giving the desired products
in good to excellent yields (Table 2, entries 6-10). o-Chloro (1f),
p-chloro (1g), o-fluoro (1h), p-fluoro (1i) and 3,4-difluoro (1j
)
substituents generated the corresponding sulfinates up to 95%
yield. Due to the steric hindrance, 1f and 1h gave lower yields,
compared to their para isomer (Table 2, entries 6 vs 7, and 8 vs
9, respectively), and dihalogen substituent led to the lowest
yield (Table 2, entry 10). Trifluoromethyl substituted benzyl
alcohol gave rise to the desired product in moderate yield
(Table 2, entry 11). Due to heavy side reaction, the reaction of
1-naphthalenemethanol (1l) afforded corresponding sulfinate
3l in yield of 22% (Table 2, entry 12).
Conv.b Yieldb
Entry
1
, R1, R2, R3, R4
3
(%)
(%)
87 (82)c
1
1a, R1 = H, R2 = H
3a 88
3b 84
2
1b, R1 = 4-Me, R2 = H
1c, R1 = 4-NO2, R2 = H
1d, R1 = 4-CN, R2 = H
1e, R1 = 4-OH, R2 = H
1f, R1 = 2-Cl, R2 = H
1g, R1 = 4-Cl, R2 = H
1h, R1 = 2-F, R2 = H
1i, R1 = 4-F, R2 = H
1j, R1 = 3,4-F, R2 = H
1k, R1 = 4-CF3, R2 = H
83 (73)
73 (69)
65 (61)
37 (36)
82 (75)
95 (92)
78 (71)
90 (80)
49 (44)
52 (45)
22 (21)
39 (34)
92 (85)
80 (74)
83 (79)
24 (21)
33 (30)
Routinely, we set out to explore various secondary alcohols
as well as allylic alcohols (Table 2, entries 13-18). The benzylic
3
3c
74
secondary alcohols, such as α-phenethyl alcohol
(1m),
4
3d 73
3e 37
benzhydrol (1n) and p-fluorobenzhydrol (1o) provided the
desired products in 39-92% yields and in the case of 1m no
significant formation of olefins was generated from
elimination of β-H, respectively (Table 2, entries 13-15). We
investigated the substitutions on different allylic alcohols as
well, the desired products were obtained in 24-83% yields and
γ-sulfinated products were not detected, resulted from the π-
bond shift (Table 2, entries 16-18).
5
6
3f
82
7
3g 98
3h 80
8
9
3i
3j
92
49
10
11
12
13
14
15
16
17
18
Table 3 Sulfination of different unactivated alcohols with sodium
sulfinate saltsa
3k 53
1l, R1 = 1-naphthyl, R2 = H 3l
93
1m, R1 = H, R2 = Me
1n, R1 = H, R2 = Ph
1o, R1 = 4-F, R2 = Ph
1p, R3 = H, R4 = H
1q, R3 = Ph, R4 = H
1r, R3 = Ph, R4 = Me
3m 95
3n 92
3o 80
3p 83
3q 90
Conv.b
(%)
Yieldb
(%)
Product 3
3s
3t
93
92
87
83
92 (86)c
91 (85)
84 (81)
80 (79)
1s
1t
3r
94
a
Reaction conditions:
(1.8 equiv), dichloromethane (1.5 mL) at 50 oC for 3 h.
1 (0.5 mmol), 2a (0.65 mmol), BF3·OEt2
b
Determined by 1H NMR spectroscopy using anisole as an
c
internal standard. Yield of isolated products shown within
parentheses.
3u
3v
1u
With the optimized reaction conditions in hand, the scope
of structurally various benzylic and allylic alcohols with sodium
p-toluenesulfinate was explored and the results were
summarized in Table 2. We firstly focused on the generality of
various benzyl alcohols (Table 2, entries 1-12). A series of
primary benzyl alcohols 1a-l were examined in the reaction
with 2a. It was found that benzyl alcohols with methyl, nitro
and cyano substitutions at the para-position presented
appreciable activities, giving the products 3a-d in good yields
(65-87%) (Table 2, entries 1-4). The sulfination with 4-
methoxybenzyl alcohol was unsuccessful, however, in the case
of p-hydroxybenzyl alcohol (1e) without OH-protection, a
moderate yield of the corresponding sulfinate 3e was obtained
(Table 2, entry 5). Benzyl alcohols with halogen substitutions
O
S
14
O
1v
3w
3x
82
85
76 (74)
83 (78)
1w
1x
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substitution of testosterone and dihydroepiandrosterone with
sodium p-toluenesulfinate and sodium benzenesulfinate,15 and
the desired steroidal sulfinates 3B-3E were obtained in high
yields without by-products. The structure of sulfinate 3D was
confirmed convincingly through single-crystal X-ray diffraction
analysis (Fig. 3). Fortunately, tertiary alcohols worked well as
expected. Due to the presence of acetylenic bond, in the case
of 1-ethynyl-1-cyclohexanol, the product 3F was given in yield
of 48% along with some unidentified by-products. In the
reaction of bulkyl 1-adamantanol with sodium p-
toluenesulfinate, the reaction efficiency was diminished
reasonablely, and solely gave the desired product in 52% yield
3y
3z
95
91
94 (87)
91 (85)
1y
1z
3A
3B
3C
64
83
82
63 (59)
82 (81)
82 (80)
(
3G).
1A
1B
2a, R =
p-Tolyl
2b, R
=Ph
2a, R =
p-Tolyl
3D
3E
81
81
81 (78)
80 (78)
2b, R
Fig. 3 X-ray crystal structure of 3D.
=Ph
1C
Upon the structure of testosterone 1B, the scope of the
reaction was also investigated by varying sodium sulfinates
and the results were given in Table 4. Sulfinate 3H was
obtained in 40% yield from sodium butyl sulfinate 2c. Chlorine
3F
96
55
48 (41)
52 (51)
and bromine substituted sodium sulfinates (2d and 2e
)
1D
provided the corresponding sulfinates 3I and 3J in 72% and
69% yields, respectively. The sodium sulfinate 2f bearing an
electron-withdrawing group required much more reaction
time, compared to the sodium sulfinate 2a, giving 3K in
moderate yield of 45%. The sodium heteroaryl sulfinate 2g
went smoothly to furnish the desired steroidal sulfinates 3L in
87% yield.
3G
1E
a
Reaction conditions: 1 (0.5 mmol), 2 (0.65 mmol), BF3·OEt2 (1.8
equiv), dichloromethane (1.5 mL) at 50 oC for 3 h. b Determined by
1H NMR spectroscopy using anisole as an internal standard. Yield
c
Table 4 Sulfination of testosterone 1B with various sodium sulfinate
saltsa
of isolated products shown within parentheses.
R
S
OH
O
Compared with benzyl carbocation, less stability exists for
aliphatic carbocation, especially for primary and secondary
ones. We explored the substrate scope of several structurally
various aliphatic alcohols with sodium sulfinates in this
sulfination, and the results are summarized in Table 3. We first
focused on substituted primary fatty alcohols. Interestingly,
linear aliphatic alcohols such as octanol, decanol, dodecanol,
hexadecanol and branched aliphatic alcohol proceeded cleanly
with sodium p-toluenesulfinate in the presence of BF3·OEt2 to
the corresponding sulfinates 3s-y in high to excellent yields
(76-94%). Inspired by these results with primary aliphatic
alcohols, we turned our attention to secondary fatty alcohols.
The sulfinations of isopropyl alcohol and cyclohexanol with
sodium p-toluenesulfinate also afforded the sulfinates
O
O
S
H
H
(1.8 eq.)
BF3— OEt2
+
R
ONa
CH2Cl2, 50 oC, 3 h
H
H
O
O
1B
2
3
Conv.b Yieldb
Entry
2
3
(%)
(%)
42
40 (38)c
1
2
3H
2c
3I
72
72 (70)
effectively (91% for 3z
, 63% for 3A). Hydroxysteroids
2d
molecules are broadly distributed in nature and induce a wide
variety of biological processes, such as proliferation,
development, and differentiation of cell. We investigated the
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Conclusions
In summary, BF3·OEt2 participated sulfination of various levels
of alcohols with sodium sulfinates has been developed, which
provided an convenient method for the synthesis of
structurally various functionalized sulfinates. We have
advanced our understanding on BF3·OEt2 participated reaction
special for reactivity of alkyl carbocation. Several highly
complex and medicinally relevant compounds have been
shown in sulfination, and series of steroidal alcohols could be
elaborated hopefully into more complex sulfinates of broad
interest.
3
3J
72
69 (66)
2e
47
88
45 (41)d
87 (85)
4
3K
3L
2f
5
2g
a
Reaction conditions: 1B (0.5 mmol), 2 (0.65 mmol), BF3·OEt2 (1.8
equiv), dichloromethane (1.5 mL) at 50 oC for 3 h. b Determined by
Acknowledgements
c
1H NMR spectroscopy using anisole as an internal standard. Yield
We thank the National Natural Science Foundation of China
(no. 21372265), the Fundamental Research Funds for the
Central Universities (no. CDJZR14225502 and no. CQDXWL-
2013-Z012), and the Chongqing University Postgraduates’
Innovation Project (No. CYS15017, J.P.).
of isolated products shown within parentheses. d 5 h.
To glean insights into the mechanism, two control
experiments were performed. In the presence of catalytic
amount (20 mol%) of BF3·OEt2, p-toulenesulfinic acid was
chosen as sulfination reagent to react directly with benzyl
o
alcohol 1a in dichloromethane at 50 C for 3 h; as a result, 3a
Notes and references
was obtained in 84% yield. Under the protection of nitrogen,
the model reaction was executed and no reaction took place,
which suggested that moisture from air of open-flask
conditions were requisite for formation of superacid BF3-H2O
and promoted conversion of sodium p-toluenesufinate into
corresponding nucleophile sulfinic acid. So BF3·OEt2 plays a
dual role in this transformation: a) catalyzing the sulfination; b)
forming BF3-H2O to neutralize the sodium sulfinate.
Accordingly, a plausible mechanism is proposed as shown in
Fig. 4. Firstly, hydroxyl moiety of benzyl alcohol is effectively
activated by the Lewis acid BF3·OEt2 through the strong
coordination to boron center. To obtain 3a, this procedure
may undergo two different pathways. Following the SN2
pathway, the nucleophilic O-attack of the p-toulenesulfinic
acid onto activated benzyl alcohol generates a transition state
1
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TS) with the bond C-OH weakened. Alternatively, benzyl
alcohol can give rise to stable carbocation more favorably due
to p-π super conjugation, thus sufination undergoes SN1
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Green Chemistry
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DOI: 10.1039/C5GC02846A
A convenient and efficient method for the synthesis of structurally various functionalized
sulfinates shows good substrate generality of alcohols and sodium sulfinates.