Electrochemical‐Induced Hydroxysulfonylation of α‐CF₃ Alkenes to Access Tertiary β‐Hydroxysulfones

Abstract

An electrochemical hydroxysulfonylation of α-CF 3 alkenes was accomplished in this work. By using easily available sodium sulfinates as the sulfonylating agents, a series of valuable α-trifluoromethyl tertiary alcohols were synthesized under mild and environmentally friendly electrolysis conditions in moderate to good yields. The preliminary mechanistic investigation indicates that this difunctional reaction involves a radical process via a sulfonyl radical. Gram-scale synthesis shows the significant potential application of this protocol.

Research Progress of Electrochemical Synthesis of C-Sulfonyl Compounds

“…该方法以碳棒作阳极, 镍作阴极, 四丁基四氟硼酸铵作电解质, 在未分隔电解 池中, 磺酰肼、烯烃 86 和醇 87 在恒定电流条件下反应 获得一系列 β-烷氧基砜化合物 88 (Scheme 33). 2020 年, 黄精美课题组 [32] 报道了一种电化学条件 下苯乙烯基酰胺 89 与磺酰肼的自由基串联环化反应合 针对两种不同的反应底物, 该课题组 [36] 2022 年, 该课题组 [38]…”

Catalyst-free electrochemical trifluoromethylation of coumarins using CF3SO2NHNHBoc as the CF3 source

“…Further optimization showed that the amount of water was important for the reaction: an 8 : 1 ratio of CH Probably, the acidic conditions in the reaction caused the decomposition of the product. Delightfully, n Bu 4 NOAc might not have only served as an electrolyte, but also as a base 43 that neutralized the protons formed in the reaction. Then, increasing or decreasing the current was tested, but led to a decrease of yields (Table 1, entries 10 and 11).…”

Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

“…Recently, a new protocol that enables the synthesis of tertiary β-hydroxysulfones ( 32 ) was developed by Lei et al 17 via the electrochemical three-component reaction of α-trifluoromethyl styrenes ( 30 ), sodium sulfonates ( 31 ) and H 2 O (Scheme 5). A range of β-trifluoromethylsulfones were assembled by varying styrenes and sodium sulfonates.…”