Visible Light Accelerated Vinyl C–H Arylation in Pd‐Catalysis: Application in the Synthesis of ortho Tetra‐substituted Vinylarene Atropisomers

Abstract

A visible light accelerated C-H functionalization reaction in palladium-catalyzed arylation of vinyl arenes with diaryliodonium salts is reported in the absence of additional photosensitizer. The kinetic isotope effect (k H /k D ) was changed from 3.6 (under darkness) to 1.1 when irradiated by visible light, which indicated that the C-H functionalization step was the rate determining step under darkness and significantly accelerated by the irradiation of visible light. Finally the synthesis of ortho tetra-substituted vinylarene atropisomers with high enantiospecificity was realized via this protocol.

Palladium‐Catalzyed Atroposelective 16‐Membered Macrocyclization: Total Synthesis of Isoplagiochin D†

“…In continuation of our research interests in transition‐metal‐ catalyzed atropisomer synthesis [ 35‐38 ] and with the inspiration of Speicher's work, [ 30‐32 ] herein we report a catalytically asymmetric macrocyclization of benzyl chlorides and N ‐Ts hydrazones. Due to the high ring‐strain, the atroposelective ring closure was obviously considered as the most challenging step.…”

Mechanochemical C−X/C−H Functionalization: An Alternative Strategic Access to Pharmaceuticals

“…The alkene‐(hetero)arenes framework features wide applications in pharmaceutical drugs, natural products as well as functional materials [28] . In the past decades, the synthetic methodologies for the preparation of vinyl‐arenes and vinyl‐heteroarenes has been extensively explored, such as Wittig‐type reaction, [29] olefin metathesis reaction, [30] Mizoroki‐Heck cross‐coupling, [31] carbene‐involved reaction, [32] and the alkynes [33] and allenes [34] functionalization.…”

Enantioselective Construction of Vicinal Diaxial Styrenes and Multiaxis System via Organocatalysis

“…Recently, axially chiral styrenes as the new member of the axially chiral family has received extensive attention from synthetic chemists . Consequently, a few examples of the enantioselective construction of axially chiral styrenes have been reported by the research groups of Baker, Miyano, Gu, , Smith, Tan and our group , (Scheme ).…”