Silver(I)-Promoted Radical Sulfonylation of Allyl/Propargyl Alcohols: Efficient Synthesis of γ-Keto Sulfones

Article abstract of DOI:10.1002/asia.201601223

An efficient Ag₂CO₃-promoted sulfonylation of allyl/propargyl alcohols with sodium sulfinates has been developed. The reaction tolerates a wide range of functional groups to deliver γ-keto sulfones in high yields (up to 93 %). Propargyl alcohols furnished trimerization product 1,3,5-triaroylbenzenes in the presence of sodium methanesulfinate under the standard conditions. A mechanism involving a sulfonyl radical was suggested.

Full text of DOI:10.1002/asia.201601223

DOI: 10.1002/asia.201601223
Communication
Sulfonylation
Silver(I)-Promoted Radical Sulfonylation of Allyl/Propargyl
Alcohols: Efficient Synthesis of g-Keto Sulfones
Guichun Fang+,[a] Jianquan Liu+,[a] Weidong Shang,[a] Qun Liu,[a] and Xihe Bi*[a, b]
Abstract: An efficient Ag2CO3-promoted sulfonylation of
allyl/propargyl alcohols with sodium sulfinates has been
developed. The reaction tolerates a wide range of func-
tional groups to deliver g-keto sulfones in high yields (up
to 93%). Propargyl alcohols furnished trimerization prod-
uct 1,3,5-triaroylbenzenes in the presence of sodium
methanesulfinate under the standard conditions. A mech-
anism involving a sulfonyl radical was suggested.
Keto sulfones are well known to be a highly valuable class of
compounds which are versatile building blocks and valuable
intermediates in organic synthesis[1] and pharmaceutical
chemistry.[2] The addition of sulfonyl radicals to unsaturated
systems such as alkenes and alkynes represents a particularly
Figure 1. Synthesis of g-keto sulfones via radical processes.
useful approach to such compounds.[3] With this strategy, vari-
ous sulfonyl radicals, generated from sulfonyl hydrazides,[4] di-
methyl sulfoxide,[5] sulfinates,[6] sulfinic acids,[7] and thiophe-
nols,[8] etc. have been successfully employed in these radical
specialized radical acceptors. Most recently, a hydrosulfonyla-
tion of chalcones with arylsulfonyl hydrazides leading to g-keto
reactions to furnish keto sulfones. Among these, the synthetic
methodologies of b-keto sulfones have been widely explored.[9]
However, compared to the rapid development of b-keto sul-
fones, the direct synthesis of g-keto sulfones in terms of sulfo-
nyl radical addition is not well documented. Recently,
a number of metal-catalyzed or metal-free protocols to con-
struct sulfonylated oxindoles from N-arylacrylamide derivatives
via a radical cascade process have been reported, which effec-
tively delivered heterocycles bearing a g-keto sulfone moiety
in high yields (Figure 1a). However, in these cases the access
to the g-keto sulfone moiety is highly limited to structurally
sulfones in good to excellent yields was reported, using
20 mol% of tetra-n-butylammonium iodide (TBAI), along with
stoichiometric amounts of benzoyl peroxide (BPO) and tert-
butyl hydroperoxide (TBHP) as co-oxidants (Figure 1b).[10] How-
ever, in comparison with the high efficiency of arylsulfonyl hy-
drazides, alkylsulfonyl hydrazides were inapplicable under the
employed conditions. Therefore, this definitely calls for the de-
velopment of a more efficient, general catalytic approach for
the synthesis of g-keto sulfones because of their potential ap-
plicability in organic synthesis and their diverse biological
properties.[11] Prompted by these facts, we report herein the
first example of an efficient Ag2CO3-promoted sulfonylation of
terminal allyl/propargyl alcohols with sodium sulfinates to
access g-keto sulfones in good to excellent yields, in which
both aryl- and alkyl-substituted sodium sulfinates resulted in
a successful transformation (Figure 1c).[12] The sulfonylation of-
fered an access to the synthesis of g-keto sulfones via a radical
route through a one-step procedure.[13,14]
[a] G. Fang,+ J. Liu,+ W. Shang, Q. Liu, Prof. X. Bi
Jilin Province Key Laboratory of Organic Functional Molecular Design &
Synthesis
Department of Chemistry
Northeast Normal University
Renmin Str. 5268#, Changchun 130024 (China)
E-mail: bixh507@nenu.edu.cn
Our initial investigation commenced with the exploratory re-
action between 1-phenylprop-2-en-1-ol (1a) and sulfinate 2a
in the presence of 30 mol% of Ag2CO3 in 1,4-dioxane at 1008C
in air.[15] Delightfully, the reaction proceeded well, furnishing
the desired product, g-keto sulfone 3a, in 76% yield (Table 1,
entry 1). Compared to Ag2CO3, other silver salts (Ag3PO4,
AgNO3, AgOTf, and AgOAc) were far less effective or even
failed in this transformation (entries 2–5). It is worth mention-
Homepage: http://www.bigroup.com.cn/
[b] Prof. X. Bi
State Key Laboratory of Elemento-Organic Chemistry
Nankai University
Tianjin 300071 (China)
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for the au-
thor(s) of this article can be found under http://dx.doi.org/10.1002/
asia.201601223.
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ring also furnished sulfone 3m in a yield of 63%. In addition,
allyl alcohols containing fused aromatic groups as well as het-
eroaromatic groups all reacted smoothly to give the desired
products (3h–j). Delightfully, the aliphatic sodium sulfinate
also possessed high reactivity under the standard conditions,
furnishing the desired product 3k in 81% yield.
Table 1. Optimization of the reaction conditions.[a]
In view of these interesting results, we further extended the
substrate scope of this strategy to propargyl alcohols
(Scheme 2). With sodium p-methylphenylsulfinate (2a) as the
Entry
Cat.
Solvent
T [8C]
Yield[b] [%]
1
2
3
4
5
6
7
8
Ag2CO3
Ag3PO4
AgNO3
AgOTf
AgOAc
–
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
DMF
Toluene
Toluene
Toluene
100
100
100
100
100
100
100
100
50
76
trace
0
0
trace
0
0
91
42
20
9
10[c]
100
[a] Reaction conditions: 1a (0.5 mmol), 2a (1.5 mmol) and the catalyst
(30 mol%) in solvent (2.0 mL) at 1008C under air atmosphere for 6 h.
[b] Isolated yield of 3a. [c] Under N2 atmosphere.
ing that no reaction was observed in the absence of silver salts
(entry 6). Further screening of solvents identified toluene as
the most suitable solvent (entries 7–8). Decreasing the reaction
temperature to 508C resulted in a significant drop in the yield
of 3a (entry 9). Interestingly, the yield of 3a considerably de-
creased to 20% under a nitrogen atmosphere (entry 10). This
observation demonstrates that dioxygen has a significant
impact on the efficiency of the process.
Once the optimal reaction conditions were established, ef-
forts were then focused on the scope of this method
(Scheme 1). A series of arylallyl alcohols 1 worked well with
various sodium sulfinates 2. A variety of electron-donating (R=
OMe or Me) or -withdrawing groups (R=Cl or F3C) at the 3- or
4-position of the aromatic ring were all compatible, affording
the expected g-keto sulfones in yields of 73–93% (3a–g). Inter-
estingly, allyl alcohols with an allyloxy group on the aromatic
Scheme 2. Sulfonylation reaction of different propargyl alcohols with
sodium sulfinates.
sulfonyl source, a variety of phenyl propargyl alcohols bearing
electron-donating or -withdrawing substituents resulted in
a smooth conversion to afford the desired products in yields of
71–92% (5a–e). Moreover, 2-naphthyl (4 f) and 2-furyl (4g) al-
kynyl carbinols also furnished good yields of g-keto sulfones
(5 f, 5g), thus further expanding the scope of this sulfonylation
reaction. It is noteworthy that trimerization was observed
when styryl alkynyl carbinol (4h) was treated under the stan-
dard conditions, although the desired product 5h was ob-
tained in a high yield (sulfonylation/trimerization=10:1, 68%
combined yield). The reaction was also tested with other
sodium arenesulfinates. As illustrated in Scheme 2, the sulfony-
lation was general with respect to structural variations on the
sodium sulfinate. Importantly, when the S-substituent on the
sodium sulfinate 2 was an aryl group, the reaction appeared to
be more effective under the standard conditions with proparg-
yl alcohol 4a than sodium methanesulfinate (MeSO2Na) (5i–
5k). However, no desired g-keto sulfones were obtained when
aliphatic alkynyl carbinols were used.
Interestingly, the treatment of the propargyl alcohols 4 with
MeSO2Na (2b) under the standard conditions allowed the tri-
merization of propargyl alcohols, furnishing 1,3,5-triaroylben-
zenes as main products (6a–d) (Scheme 3). The transition-
Scheme 1. Sulfonylation reaction of different allyl alcohols with sodium sulfi-
nates.
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Scheme 3. Trimerization of propargyl alcohols with sodium methanesulfinate
to access 1,3,5-triaroylbenzenes.
metal-catalyzed [2+2+2] cycloaddition of alkynes has been re-
garded as one of the most classical processes to prepare ben-
zenes and analogous aryl derivatives.[16] Generally, the 1,3,5-tri-
aroylbenzene skeletons are constructed by base-catalyzed Mi-
chael-type cyclotrimerization of the corresponding 1-aryl-2-
propyn-1-ones.[17] In comparison with the alkynyl ketones, reac-
tions of propargyl alcohols as the starting material require mul-
tiple steps.[18] Remarkably, the present strategy appears to be
a straightforward and selective route to access 1,3,5-triaroyl-
benzenes in a single-step operation. The formation of such
compounds could be attributed to the sulfonyl radical-induced
[2+2+2] cycloaddition of propargyl alcohols 4.[19] It is worth
noting that the reaction proceeded without pre-oxidation of
propargyl alcohols.[20] Consequently, the radical protocol de-
scribed here, starting from propargyl alcohols, constitutes
a novel and concise approach to synthesize 1,3,5-triaroylben-
zenes.
Scheme 4. Mechanism investigations.
Treatment of a-deuterated propargyl alcohol D-4a under stan-
dard conditions resulted in 81% yield of 5a, without deuterat-
ed product observed [Eq. (5)], which suggested that the a-H of
propargyl alcohol 4a was not the source of the olefinic hydro-
gen of product 5a.
To probe the plausible mechanistic pathway for this reaction,
several control experiments were designed and performed
(Scheme 4). Based on literature studies,[3c] a radical trapping ex-
periment was initiated. In the presence of 2,2,6,6-tetramethyl-
1-piperidinyloxy (TEMPO) (2.0 equiv), under the standard condi-
tions, the formation of g-keto sulfone 5a was completely sup-
pressed, which indicates that the reaction probably proceeds
through a radical pathway [Eq. (1)]. Additionally, under optimal
conditions, b-hydroxy sulfone 6 was not oxidized to form the
corresponding g-keto sulfone 5a, implying that it was not the
intermediate in the transformation [Eq. (2)]. When 1-
phenylprop-2-yn-1-one 7 was treated under the stan-
dard conditions, no expected sulfonylated product
5a was observed [Eq. (3)]. This observation demon-
strated that the hydroxyl group played a vital role in
the success of this transformation. Moreover, a step-
wise mechanism, involving oxidation of the hydroxyl
group and subsequent Michael addition of the sulfo-
nyl radical to an alkynone intermediate, was exclud-
ed. Furthermore, a deuterium-labeling experiment
was performed. When D2O was added into the reac-
tion system of substrate 4d, the a,b-dideuterated sul-
fonylation product D-5d was obtained in 73% yield,
with 70% deuterium incorporation [Eq. (4)]. This
result implied that an organosilver intermediate
A plausible mechanism was devised for the current system,
based on literature precedence and the above-mentioned re-
sults (Scheme 5).[6b,7a,9b,21] First, a sulfonyl radical is generated
by silver catalysis. Subsequently, this radical attacks the triple
bond of acetylenic silver species A, which is generated from
the interaction of propargyl alcohol with silver(I) catalyst, to
furnish vinyl radical intermediate B. The radical B abstracts the
hydrogen atom on the adjacent hydroxyl group to generate
the oxyl radical C, which undergoes hydrogen radical abstrac-
tion to generate the C=O bond.[6b,22] Finally, protonation of the
might be generated during the reaction process. Scheme 5. A plausible reaction mechanism.
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vinyl silver(I) D affords the desired product 5a, along with re-
leasing the silver(I) catalyst.
In summary, we have developed a mechanistically novel re-
action for the synthesis of g-keto sulfones by the silver(I)-based
sulfonylation of various allyl/propargyl alcohols with sodium
sulfinates. The scope of allyl/propargyl alcohols and sodium
sulfinates is broad to deliver structurally diverse g-keto sul-
fones in good to excellent yields. Mechanistic investigations
unraveled that the process plausibly involved sequential sulfo-
nyl radical addition to a CÀC triple/double bond and a hydro-
gen atom transfer. Furthermore, 1,3,5-triaroylbenzene deriva-
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this protocol when sodium methanesulfinate is used as radical
source. Further mechanistic details and applications of this sul-
fonylation protocol are currently ongoing in our laboratory.
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Experimental Section
General Procedure for the Synthesis of Compounds 3 and 5
(with 3a as an example): A screw-capped reaction vial was charged
with allyl alcohol 1a (67 mg, 0.5 mmol) and sodium sulfinate 2a
(133.5 mg, 0.75 mmol) in toluene (2.0 mL) and stirred at room tem-
perature. Subsequently, Ag2CO3 (41.4 mg, 0.15 mmol) was added.
The reaction mixture was stirred at 1008C until the substrate 1a
was completely consumed as indicated by thin-layer chromatogra-
phy (TLC). The resulting mixture was concentrated and the residue
was taken up in ethyl acetate. The organic layer was dried over
MgSO4 and concentrated. Purification of the crude product by
flash column chromatography on silica gel afforded the corre-
sponding g-keto sulfone 3a in 91% yield.
Acknowledgements
This work was supported by the NSFC (21522202, 21502017,
21372038), the Ministry of Education of the People’s Republic
of China (NCET-13-0714), the Jilin Provincial Research Founda-
tion for Basic Research (20140519008JH), Fundamental Re-
search Funds for the Central Universities (2412015J005,
2412015KJ013), and the Jilin Province Key Laboratory of Organ-
ic Functional Molecular Design & Synthesis (No. 130028658).
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Keywords: allyl/propargyl alcohols · gamma-keto sulfones ·
radical sulfonylation · reaction mechanisms · silver catalysis
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Manuscript received: September 3, 2016
Final Article published: && &&, 0000
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COMMUNICATION
Sulfonylation
Guichun Fang, Jianquan Liu,
Weidong Shang, Qun Liu, Xihe Bi*
&& – &&
Silver(I)-Promoted Radical
Sulfonylation of Allyl/Propargyl
Alcohols: Efficient Synthesis of g-Keto
Sulfones
At the terminal: The first example of sil-
ver(I)-catalyzed radical sulfonylation of
terminal allyl/propargyl alcohols to
access g-keto sulfones with aryl- and
alkyl-substituted sodium sulfonates is
reported. A mechanism involving a sulfo-
nyl radical insertion is suggested.
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