A mild light-induced cleavage of the S-O bond of aryl sulfonate esters enables efficient sulfonylation of vinylarenes

Article abstract of DOI:10.1039/C8SC02769B

A new mode of S-O bond activation has been discovered, which constitutes novel reactivity of easily available and bench-stable arylsulfonate phenol esters. This protocol enables access to putative sulfonyl radical intermediates, which enable straightforward access to valuable vinyl sulfones.

Full text of DOI:10.1039/C8SC02769B

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A Mild Light-Induced Cleavage of SꢀO Bond of Aryl Sulfonate
Esters Enables Efficient Sulfonylation of Vinylarenes
Received 00th January 20xx,
Accepted 00th January 20xx
Maxim Ratushnyy, Monika Kamenova, and Vladimir Gevorgyan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract:
A new mode of SꢀO bond activation has been
discovered, which constitutes novel reactivity of easily available
and bench stable arylsulfonate phenol esters. This novel protocol
enables access to putative sulfonyl radical intermediates, which
empower straightforward access to valuable vinyl sulfones.
Aryl sulfonate phenol esters are versatile synthetic
intermediates in organic chemistry.
A facile CꢀO bond
cleavage under transition metal (TM)-catalyzed conditions
makes them valuable alternatives to aryl halides in cross-
coupling reactions (Scheme 1, a)1. Meanwhile, the robustness
of arylsulfonate groups under variety of reaction conditions
renders them useful protecting groups of phenols (Scheme 2,
b).2 In both scenarios, different forms of organosulfur
byproducts are discarded. Ability to utilize these intermediates
as sulfonylating reagents, on another hand, would offer an
attractive alternative strategy toward incorporation of
organosulfur motifs into organic molecules.3 Herein we report
Scheme 1 Diverse reactivity of arylsulfonate phenol esters.
mild, light-induced TM-free activation of Sꢀ
O bond4 of aryl
sulfonate phenol esters leading to the formation of putative
sulfonyl radicals.5,9 Thus the generated reactive sulfone species
add across the double bond of vinyl arenes an -heteroarenes
to furnish valuable vinyl sulfones (Scheme 1c).
reactivity of arylsulfonate phenol esters and inspired by the
importance of vinyl sulfones,8,9 we performed an optimization
of this interesting transformation.10 It was found that tosylate
of commercially available meta-CF3 phenol is the best source
of tosyl group. The reaction proceeds best under 427 nm
visible light irradiation of 0.1 M DMA solution in the presence
of 3 equiv. of Cs2CO3 (entry 1). Introducing other electron-rich
or –deficient substituents across the phenolic aromatic ring led
to diminished yields (entries 2-5). Derivative of aliphatic
alcohol showed no reactivity, thus indicating the necessity of
an aromatic ester for the successful transformation (entry 6).
Employment of DMSO instead of DMA was equally efficient
(entry 7). Switching to other solvents commonly used in radical
chemistry was not productive (entries 8-10). Lowering amount
of base played a detrimental role, as well (entry 11) Addition
of radical scavengers such as TEMPO or galvinoxyl completely
suppressed this sulfonylation reaction (entries 12-13). Finally,
the test experiment indicated that this reaction does not
proceed in the absence of light (entry 14).
Within the framework of our ongoing studies on the
development of light-induced synthetic methodologies,6 we
unexpectedly discovered a sulfonylation of styrene 1a with
arylsulfonate phenol ester 2a into vinyl sulfone 3a (Table 1).
Vinyl sulfones have received considerable attention in recent
years, as these motifs are featured in medicinally relevant
structures,7 and also serve as useful reactive intermediates.8
Most of the established protocols toward synthesis of vinyl
sulfones rely on employment of TM-catalysts and/or utilizing
excessive amounts of oxidants.9 In contrast, the observed
sulfonylation reaction takes advantage of mild light-induced
activation of SꢀO bond, thus potentially providing alternative
route toward vinyl sulfones. Intrigued by the uncovered novel
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1 Optimization of reaction parameters.a
Next, the scope of the sulfone moiety was examined (Table
3). Gratifyingly, diverse substitution patterns on arylsulfonate
phenol esters possessed no problem for the developed
Table 2 Scope of vinyl arenes.a
Entry
1
Deviation from standard conditions
none
Yield, %b
90
40
16
78
10
0
2
2b instead of 2a
3
2c instead of 2a
4
2d instead of 2a
5
2e instead of 2a
6
2f instead of 2a
7
DMSO instead of DMA
PhH instead of DMA
PhCF3 instead of DMA
MeCN instead of DMA
Cs2CO3 (2 equiv.) instead of Cs2CO3 (3 equiv.)
galvinoxyl (2 equiv)
TEMPO (2 equiv)
89
0
8
9
0
10
11
12
13
14
15
64
0
0
no light, 60 to 100 ℃
0
89
a Reaction conditions: 1a (0.1 mmol), 2a (0.3 mmol), Cs2CO3 (0.3 mmol), DMA (0.1 M),
40 W 427 nm LED. b GC/MS yield.
The study on the generality of this transformation of this
sulfonylation reaction (Table 2) showed that styrenes
a Reaction conditions: 1 (0.1 mmol), 2 (0.3 mmol), Cs2CO3 (0.3 mmol), DMA (0.1 M), 40
W 427 nm LED. b 450 nm LED
possessing electron-releasing (1b) and –withdrawing (1c, d)
substituents at the para position all reacted well to give the
corresponding vinyl sulfones in good yields. Pleasingly, Bpin
moiety-containing 1e was compatible with the reaction
conditions delivering vinyl sulfone 3e in 62% yield. Substitution
at the ortho- (3f), and meta- (3g) positions posed no problem,
as well. Various vinyl heteroarenes were found to be capable
partners in this sulfonylation reaction. Thus fused N-, O- and S-
containing vinylarenes provided corresponding products 3h-3k
efficiently. This protocol also works with vinyl pyridines,
producing 3l-3n in excellent yields. The scale-up experiment
proceeded smoothly to deliver vinyl sulfone 3l in 81% yield.
Notably, mild reaction conditions provided N-sulfonyl vinyl
imidazole (3o) in good yield. Importantly, this reaction can also
be carried out with disubstituted styrenes to produce various
trisubstituted sulfones 3p-3r in reasonable to good yields.
Moreover, this reaction can be accomplished in a more
complex setting to give access to vinyl sulfone derivative of
estrone (3s).
Table 3 Scope of aryl sulfonate esters.a
2 | J. Name., 2012, 00, 1-3
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producing alkylsulfone
7
in good yield. Versatility of the
obtained vinyl sulfones may be further exemplified by
transformations toward 11, which have been featured in
reported protocols.21,22,23,24
a Reaction conditions: 1 (0.1 mmol), 2 (0.3 mmol), Cs2CO3 (0.3 mmol), DMA (0.1 M), 40
8-
W 427 nm LED.
protocol providing excellent yields of the respective vinyl
sulfones 3t-3x. Importantly, this protocol may successfully be
applied
toward
sulfone
3y
featuring
3,5-
bis(trifluoromethyl)phenylsulfone fragment, a very useful
synthon for the transition metal-catalyzed coupling
reactions,11 as well as for the modified Julia olefination
reaction.12 Heteroaryl sulfonates also participated well leading
to products 3aa, 3ab in 95 and 69% yields, respectively.
The proposed mechanism of this sulfonylation reaction is
depicted in the Scheme 2. The base-assisted13 formation of an
electron donor-acceptor (EDA) complex14
A
between
and molecule of DMA occurs
first.15 Upon excitation, this complex (A*) undergoes a single
electron transfer (SET)16 leading to radical anion
, which
fragments into sulfonyl radical and phenoxide . Addition of
sulfonyl radical . In one
to styrene5d produces benzyl radical
scenario, the latter experiences intermolecular hydrogen atom
transfer (HAT) with sulfonyl radical , formed in parallel by
cleavage of the S O bond (
17 or, alternatively, with the
radical , formed during the first SET step (A* ), to produce
arylsulfonate phenol ester
2
B
D
E
Scheme 3 Transformations of obtained vinyl sulfones. Conditions: a) 3z (0.1 mmol),
pyrrolidine (2.4 mmol), 70 ℃. b) 3z (0.1 mmol), BnSH (0.4 mmol), Et3N (0.15 mmol),
MeOH (0.25 M), rt c) 3z (0.1 mmol), (TMS)3SiH (0.3 mmol), AIBN (0.25 mmol), benzene
(0.05 M), reflux d) 3y (0.1 mmol), Pd/C (0.005 mmol), hydrogen gas (balloon).
D
F
D
ꢀ
B→D+E)
C
→B
Conclusions
the reaction product, vinyl sulfone 3a. Alternatively, the
electron catalysis may be operative.18 In that case,
In summary, we have uncovered a novel reactivity of
arylsulfonate phenol esters, featuring mild visible light-induced
deprotonation of
F
produces anion-radical
G, which after
cleavage of SꢀO bond, which gives rise to putative sulfonyl
intermolecular SET with
2
produces 3a and radical-anion B,
which closes the catalytic cycle.19
radicals. The latter are capable of addition across various
aromatic and heteroaromatic alkenes providing valuable vinyl
sulfones. It is believed that this novel reactivity of arylsulfonate
esters will find application in synthesis.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgements
This work was supported by the National Institutes of Health
(GM120281) and the National Science Foundation (CHE-
1663779).
Notes and references
Scheme 2 Proposed reaction mechanism.
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A new mode of S−O bond activation has been discovered, which constitutes novel
reactivity of easily available and bench stable arylsulfonate phenol esters. This novel
protocol enables access to putative sulfonyl radical intermediates, which empower
straightforward access to valuable vinyl sulfones.