Copper-Catalyzed Intermolecular Reductive Radical Difluoroalkylation–Thiolation of Aryl Alkenes

Abstract

A novel radical-involved alkene difunctionalization catalyzed by the copper/Bpin system has been developed, leading to the difluoroalkylation-thiolation of aryl alkenes. The use of Bpin as an organic reductant enables the simultaneous installation of a C(sp)-C(FR) bond and a C(sp)-S(R) bond across the C═C bond of aryl alkenes by utilizing two electrophilic reactants. The reaction exhibits broad substrate scope, excellent diastereoselectivity, and moderate to good yields. Moreover, the reaction can be conducted on a gram scale with good yield achieved.

Cs2CO3‐Mediated Vicinal Thiosulfonylation of 1,1‐Dibromo‐1‐Alkenes with Thiosulfonates: An Expedient Synthesis of (E)‐1,2‐Thiosulfonylethenes

“…Among a variety of organosulfur compounds, thiosulfonates (RS−SO 2 R 1 ) are the privileged class of compounds in synthetic organic chemistry . Generally, thiosulfonates were demonstrated as a electrophilic sulfenylating reagent, which often discard the sulfonyl moiety as a waste ,. Recently, the diverse reactivity of thiosulfonates have been discovered as a 1,1‐ or 1,2‐thiosulfonylating agent .…”

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Nucleophilic substitution with a thiosulfonate ( 7 ) on 318 delivers a trifluoromethyl‐thiolated alkane ( 314 ) reaction product. As styrenes ( 265 ) were not compatible with these conditions, a Cu catalyst with superstoichiometric B 2 pin 2 was envisioned to achieve a radical (ethoxycarbonyl)(difluoro)alkylation–thiolation (route 2) . An SET process between BrCF 2 CO 2 Et ( 319 ) and a Cu(I)‐Bpin intermediate, formed in situ from CuTc/B 2 pin 2 with the aid of a base, generates a .…”

Intermolecular Aminoallylation of Alkenes Using Allyl‐Oxyphthalimide Derivatives: A Case Study in Radical Polarity Effects

“…Methods that achieve the difunctionalization of alkenes are particularly powerful as they rapidly introduce molecular complexity from abundant olefin starting materials in a single synthetic step Seminal work by Kharasch and co‐workers demonstrated the difunctionalization of unactivated alkenes via atom transfer radical addition (ATRA) using simple halogenated reagents (Scheme A) . This work paved the way for the subsequent development of a sophisticated class of radical‐mediated alkene difunctionalization methodologies invoking ATRA .…”