Construction of axially chiral compounds via catalytic asymmetric radical reaction

The chemistry of axially chiral compounds has emerged as a subject of increasing interest due to their widespread presence in natural products,bioactive molecules,advanced materials,and chiral ligands/catalysts.On the other hand,catalytic asymmetric radical-based transformations provide a complementary platform for the construction of enantiomerically enriched molecules that are in growing demand in the chemical and pharmaceutical in-dustries.In recent years,considerable research efforts have been devoted to the development of catalytic asymmetric radical reactions for the construction of axially chiral compounds based on the unique reactivity modes of diverse radicals.In this review,we critically illustrate these recent achievements according to different radical precursors and catalytic activation modes.Wherever possible,special emphasis is also placed on the discussion of mechanistic features underlying these works and substrate scopes.This review should be of great interest to the experts in this area,but also serve as a helpful starting point for new researchers in this field.

Rhodium(III)-Catalyzed Atroposelective C-H Indolylization of 1-Aryl Isoquinolines with 3-Indolylphenyliodonium Salts

Rhodium(III)-catalyzed enantioselective C-H indolylization of isoquinolines was developed.The C-H coupling reactions between 1-aryl isoquinoline derivatives and 3-indolylphenyliodonium salts proceeded smoothly in the presence of a modified chiral cyclopentadienyl-Rh(III)complex,affording a series of axially chiral indolylated biaryl products in excellent yields and enantioselectivity(up to 98%yield and 95%ee).