4
GONG ET AL.
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be reduced to O2−. at the cathode.
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Based on the above results and the previous reports,[10]
a
plausible mechanism for this electorchemical oxidative cross-
coupling is proposed in Scheme 5. First, the sulfur radical
was formed by the oxidation and deprotonation of 1a. The
sulfur radical undergoes homocoupling to form a disulfide
3a-1 disulfide then undergoes a further one-electron oxidation
to form a disulfide radical cation I. O2 is reduced at the cath-
−.
ode to form O2 , which reacts with the intermediate I to pro-
duce intermediate II. After that, methanol addition to II
produces intermediate III, which then releases sulfide anion
V and intermediate IV. By getting a proton, V becames 1a,
while IV was reduced at the cathode to form the final product
3a. At the same time, the hydroxide radical can get a hydro-
gen atom to become H2O and 1a can get the sulfur radical.
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1 | CONCLUSIONS
In summary, we have demonstrated an efficient and new
method for the synthesis of sulfinic esters via
electorchemical intermolecular oxidative cross-coupling
between alcohols and thiophenols. A wide variety of func-
tional groups are compatible with this metal-free protocol,
which can be carried out on a gram scale easily. A prelimi-
nary mechanistic study indicated that the reaction involves
cathodic reduction of oxygen to produce superoxide ions
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (21702081, 21702150) and China Post-
doctoral Science Foundation (BX201600114, 2016M6
02340).
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ORCID
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