Bismuth(III) bromide-catalysed substitution of benzyl alcohols with arylsulfonylmethyl isocyanides: An unexpected access to sulfinates

Article abstract of DOI:10.1002/adsc.201401173

A bismuth(III) bromide-catalysed direct substitution of benzyl alcohols with arylsulfonylmethyl isocyanides affords sulfinates under mild acidic conditions. An unforeseen reversed reactivity was observed in this highly selective formation of sulfinates instead of the formation of the usually favoured sulfones. Cytotoxicity tests (in vitro) indicated that the sulfinates exhibit antibiotic activity against a human leukaemia cell line HL-60, which would widen the structural diversity of this antitumour target and confirm the perspectives of further investigations.

Full text of DOI:10.1002/adsc.201401173

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DOI: 10.1002/adsc.201401173
Bismuth(III) Bromide-Catalysed Substitution of Benzyl Alcohols
with Arylsulfonylmethyl Isocyanides: An Unexpected Access to
Sulfinates
Hui-Jing Li,a,b Rui Wang,a Jing Gao,a Yuan-Yuan Wang,a Dong-Hui Luo,a
and Yan-Chao Wua,*
a
School of Marine Science and Technology, Harbin Institute of Technology at Weihai, Shandong 264209, Peopleꢀs Republic
of China
Fax : (+86)-631-568-7230; phone: (+86)-631-568-7230; e-mail: ycwu@iccas.ac.cn
Beijing National Laboratory for Molecular Sciences (BNLMS), and Key Laboratory of Molecular Recognition and
b
Function, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, Peopleꢀs Republic of China
Received: December 18, 2014; Revised: February 25, 2015; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201401173.
Abstract: A bismuth(III) bromide-catalysed direct
substitution of benzyl alcohols with arylsulfonyl-
methyl isocyanides affords sulfinates under mild
acidic conditions. An unforeseen reversed reactivity
was observed in this highly selective formation of
sulfinates instead of the formation of the usually
favoured sulfones. Cytotoxicity tests (in vitro) indi-
cated that the sulfinates exhibit antibiotic activity
against a human leukaemia cell line HL-60, which
would widen the structural diversity of this antitu-
mour target and confirm the perspectives of further
investigations.
formations.[4d] Considering that an intramolecular pro-
cess is usually easier than the corresponding intermo-
lecular process, the sulfonylation of benzyl alcohols
with arylsulfonylmethyl isocyanides might be practical
À
via a facile reversible isocyanide insertion into the O
H bond of benzyl alcohols,[5] followed by a potential
intramolecular ring rearrangement[6] (Scheme 1b).
To probe the feasibility of this hypothesis, we first
evaluated the reaction using 3,5-difluorobenzyl alco-
hol (1a) with para-toluenesulfonylmethyl isocyanide
(TosMIC, 2a) as the model substrates (Table 1). Reac-
tion of 1a with 2a in the presence of 10 mol% of
Bi(OTf)3 in nitromethane (CH3NO2) at 608C for
1 day did not afford sulfone 4a. Surprisingly, sulfinate
5a instead was unexpectedly obtained, albeit in only
Keywords: benzyl alcohols; bismuth; selectivity;
substitution; sulfonates
Substitution of alcohols is an important and wide-
spread chemical reaction in organic synthesis. As the
hydroxy group is a poor leaving group, substitution of
an alcohol traditionally consists of functionalisation of
the hydroxy group to furnish a latent leaving group,
and subsequently substitution of the resulting alcohol
derivative with an appropriate nucleophile.[1] The re-
alisation of a direct substitution of various alcohols is
a long-standing challenge and has been a subject of
consistent interest for organic chemists.[2,3] Direct sul-
fonylation of strongly activated alcohols,[4] such as
Baylis–Hillman alcohols and diarylmethanols, with
sulfonyl nucleophiles, such as sulfinate salts[4a,b,f] and
para-toluenesulfonylmethyl isocyanide,[4d] has been
well developed (Scheme 1a). Unfortunately, benzyl al-
cohols, as relatively less activated alcohols, were
Scheme 1. Possibilities for direct substitution of some alco-
found not to be appropriate substrates in these trans- hols.
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Hui-Jing Li et al.
Table 1. Optimization of reaction conditions for the substitution of 3,5-difluorobenzyl alcohol (1a) with TosMIC (2a).[a]
Entry
Catalyst
Additive
Solvent
Temperature
Yield [%]
1
2
3
4
5
6
7
8
Bi(OTf)3
Sc(OTf)3
In(OTf)3
Hf(OTf)4
Fe(OTf)3
Cu(OTf)2
Zn(OTf)2
Yb(OTf)3
Bi(NO3)3
BiCl3
BiI3
BiBr3
BiBr3
BiBr3
BiBr3
BiBr3
BiBr3
BiBr3
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
THF
608C
608C
608C
608C
608C
608C
608C
608C
608C
608C
608C
608C
408C
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
38
24
17
22
13
14
7
15
54
43
42
59
31
22
11
20
trace
trace
trace
trace
9
71
69
0
51
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25[b]
26[c]
DMF
CH3CN
CH3OH
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
BiBr3
BiBr3
BiBr3
BiBr3
KPF6
H3PO4
AcOH
AcOH
AcOH
AcOH
AcOH
BiBr3
408C
r.t.
r.t.
BiBr3
BiBr3
r.t.
0
[a]
General conditions: 1a (1.0 equiv.), 2a (1.5 equiv.) and catalyst (10 mol%) in solvent (c=0.2M) for 1 day.
BiBr3 (5 mol%) was used.
Sodium para-toluenesulfinate (1.5 equiv.) was used instead of TosMIC.
[b]
[c]
38% yield (entry 1). From the structure of sulfinate tion temperatures were decreased from 608C to room
5a, it seemed that instead of undergoing the envi- temperature (entries 12–14). The reaction could take
sioned intramolecular six-membered ring rearrange- place in dichloromethane or tetrahydrofuran (THF)
ment (Scheme 1b), a potential intramolecular seven- at room temperature, while nitromethane appeared to
membered ring rearrangement[7] (Scheme 1c) argua- be the most appropriate solvent (entries 14–19). Addi-
bly took place and thereby exhibited a reversed selec- tion of potassium hexafluorophosphate (KPF6,
tivity.[4d] The spatial arrangement in the latter rear- 1.0 equiv.) or phosphoric acid (H3PO4, 1.0 equiv.) as
rangement minimised indeed the unfavourable steric the additive did not provide any better results
hindrance, and thus facilitated the seven-membered (entry 14 and entries 20 and 21). Fortuitously, with
ring rearrangement. Considering the importance of acetic acid (AcOH, 1.0 equiv.) as the additive, the re-
sulfinates in synthetic chemistry,[8,9] we then turned to action proceeded smoothly at room temperature to
optimising the reaction conditions for the synthesis of afford sulfinate 5a with an excellent yield (entry 22).
sulfinate 5a.
No better result was obtained when this reaction was
With the use of other triflate salts in comparison to performed at a higher temperature (entries 22 and
Bi(OTf)3, relatively lower yields were observed under 23). The reaction did not work in the absence of
otherwise the same conditions (Table 1, entries 1–8). BiBr3, indicating that acetic acid itself is not an effec-
Further parameter optimisation identified BiBr3 as tive promoter (entries 22 and 24). The yield of 5a was
the most effective bismuth catalyst (entries 1 and 9– decreased to 51% when the loading of BiBr3 was de-
12). Decreased yields were observed when the reac- creased from 10 mol% to 5 mol% (entry 25). The re-
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Bismuth(III) Bromide-Catalysed Substitution of Benzyl Alcohols
Table 2. Sulfination of benzyl alcohols with TosMIC.[a]
action did not take place when sodium para-toluene-
sulfinate was used instead of TosMIC (2a) under oth-
erwise the same conditions, indicating that sulfinate
anions are not effective sulfinate nucleophiles for this
reaction (entries 22 and 26). Usually, sulfinate salts
were used as common weak sulfonyl nucleophiles for
the substitution of benzyl bromides,[10] allylic
amines,[11] allylic alcohols,[4] alcohol derivatives[12]
under harsh conditions. To our delight, sulfinate 5a
can be accessed by substitution of benzyl alcohol 1a
with arylsulfonylmethyl isocyanide 2a under mild
acidic conditions. Although we are not able at this
time to accurately explain the underlying mechanism
of this reaction, the mild conditions might help to pre-
vent the departure of the hydroxy group of benzyl al-
cohol 1a in the presence of BiBr3 that helped to acti-
À
vate the benzylic C O bond of intermediate 3a
(Scheme 1c). Moreover, acetic acid appeared to serve
the role of activating the imine moiety of intermedi-
ate 3a (Scheme 1c).
With the optimized reaction conditions in hand, the
scope of the reaction was subsequently investigated,
and the representative results are summarised in
Table 2. With the aromatic ring of benzyl alcohols
bearing weak electron-withdrawing groups such as
fluoro, chloro and bromo, benzyl alcohols 1a--f react-
ed smoothly with arylsulfonylmethyl isocyanide 2a in
the presence of BiBr3 (10 mol%) and AcOH
(1.0 equiv.) at room temperature to afford sulfinates
5a–f in good to excellent yields within 1 day (en-
tries 1–6). With a strong electron-withdrawing group
such as a trifluoromethyl group at the aromatic ring
of the benzyl alcohol, benzyl alcohol 1g reacted
equally well with arylsulfonylmethyl isocyanide 2a
under the standard conditions to give sulfinate 5g in
70% yield (entry 7). Sulfination of an unsubstituted
benzyl alcohol (1h) with arylsulfonylmethyl isocya-
nide 2a under the standard conditions generated sulfi-
nate 5h in 56% yield (entry 8). With electron-donat-
ing groups, such as methyl (a weak electron-donating
group) and phenoxy (a strong electron-donating
group), at the aromatic ring of benzyl alcohols, substi-
tution of benzyl alcohols 1i and j with arylsulfonyl-
methyl isocyanide 2a under the standard conditions
afforded sulfinates 5i and j in moderate yields (en-
tries 9 and 10). Reaction of 1-phenylethanol (1k) with
arylsulfonylmethyl isocyanide 2a under the standard
conditions generated sulfinate 5k in 47% yield
(entry 11). By treating (S)-(À)-1-phenylethanol with
arylsulfonylmethyl isocyanide 2a under otherwise
[a]
General conditions: 1 (0.2 mmol), 2a (59.7 mg, 0.3 mmol),
BiBr3 (9.1 mg, 0.02 mmol) and AcOH (3.7 mL, 0.2 mmol)
in CH3NO2 (1 mL) at room temperature for 1 day.
Sulfination of different alcohols with arylsulfonyl-
identical conditions, chiral sulfinate 5k was obtained methyl isocyanides were next investigated (Table 3).
with an excellent enantioselectivity (>99% ee, see the Sterically hindered arylsulfonylmethyl isocyanide 2b
Supporting Information for the HPLC traces). The reacted with benzyl alcohol 1a in the presence of
isolation of chiral sulfinate 5k indicates that this reac- BiBr3 (10 mol%) and AcOH (1.0 equiv.) at room tem-
tion occurs by an SN2 mechanism, supporting the pro- perature to afford sulfinate 5a in 60% yield within
posed intramolecular ring rearrangement, which in- 1 day (entry 1). By treatment of arylsulfonylmethyl
volves an SN2-type nucleophilic substitution.
isocyanide 2c with benzyl alcohol 1g under the stan-
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Table 3. Sulfination of alcohols with arylsulfonylmethyl iso-
Experimental Section
cyanides.[a]
Procedure for the Sulfination of Benzyl Alcohols with
Arylsulfonylmethyl Isocyanides
The mixture of 3,5-difluorobenzyl alcohol (1a, 23.8 mL,
0.2 mmol), para-toluenesulfonylmethyl isocyanide (TosMIC,
2a, 59.7 mg, 0.3 mmol), bismuth bromide (BiBr3, 99%,
9.1 mg, 0.02 mmol) and acetic acid (AcOH, 3.7 mL,
0.2 mmol) in nitromethane (CH3NO2, 1 mL) under argon
was stirred at room temperature for 1 day, and added with
water (5 mL) and ethyl acetate (10 mL). The two layers
were separated, and the aqueous phase was extracted with
ethyl acetate (3ꢂ10 mL). The combined organic extracts
were washed by brine, dried over anhydrous sodium sulfi-
nate, filtered, and concentrated. The residue was purified by
flash chromatography on silica gel (100–200 mesh) to afford
1
sulfinate 5a as a yellow liquid; yield: 40 mg (71%). H NMR
(400 MHz, CDCl3): d=7.63 (d, J=8.0 Hz, 2H), 7.35 (d, J=
8.0 Hz, 2H), 6.78–6.70 (m, 3H), 4.95 (d, J=12.3 Hz, 1H),
4.49 (d, J=12.3 Hz, 1H), 2.44 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=162.9 (dd, JC,F =330.2, 16.7 Hz, 1C), 143.3,
141.2, 139.6 (t, JC,F =12.2 Hz, 1C), 129.8, 125.3, 110.8 (dd,
J
C,F =23.0, 10.8 Hz, 1C), 103.6 (t, JC,F =33.4 Hz, 1C), 63.6,
21.5; FT-IR (film): n=1629, 1599, 1464, 1368, 1323, 1137,
1119, 946, 854, 813, 759, 673 cmÀ1; HR-MS (ESI): m/z=
305.0416, calcd. for C14H12F2NaO2S [M+Na]+: 305.0418.
[a]
General conditions: 1 (0.2 mmol), 2 (0.3 mmol), BiBr3
(9.1 mg, 0.02 mmol) and AcOH (3.7 mL, 0.2 mmol) in
CH3NO2 (1 mL) at room temperature for 1 day.
Acknowledgements
This work was supported by the Science and Technology De-
velopment Project of Weihai (No. 2011DXGJ13,
2012DXGJ02), the Science and Technology Development
Project of Shandong (No. 2013GGA10075), and the National
Natural Science Foundation of China (No. 21202028,
21372054).
dard conditions, sulfinate 5l was obtained in 70%
yield (entry 2). Methallyl alcohol (1l) and cinnamyl al-
cohol (1m) have also been investigated; they reacted
with arylsulfonylmethyl isocyanide 2a under the stan-
dard conditions to afford sulfinates 5m and n in good
yields (entries 3 and 4). Furthermore, phenethyl alco-
hol (1n), a non-activated alkyl alcohol, reacted with
arylsulfonylmethyl isocyanide 2a uneventfully to give
sulfinate 5o in 53% yield (entry 5).
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COMMUNICATIONS
6 Bismuth(III) Bromide-Catalysed Substitution of Benzyl
Alcohols with Arylsulfonylmethyl Isocyanides: An
Unexpected Access to Sulfinates
Adv. Synth. Catal. 2015, 357, 1 – 6
Hui-Jing Li, Rui Wang, Jing Gao, Yuan-Yuan Wang,
Dong-Hui Luo, Yan-Chao Wu*
6
asc.wiley-vch.de
ꢁ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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These are not the final page numbers!