A new chiral Brønsted acid, generated in situ from a chiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This “designer acid catalyst”, which is more acidic than TsOH as suggested by DFT calculations, allows the unprecedented direct asymmetric reduction of C2‐aryl‐substituted N‐unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance. DFT calculations and mechanistic experiments indicates that this reaction undergoes C3‐protonation and hydride‐transfer processes. Besides, bulky C2‐alkyl‐substituted N‐unprotected indoles are also suitable for this system.

The transition-metal-catalyzed allylation reaction is an efficient strategy for the construction of new carbon–carbon bonds alongside allyl or homoallylic functionalization. Herein we describe a Ni-catalyzed reductive allylation of α-chloroboronates to efficiently render the corresponding homoallylic boronates, which could be readily converted into valuable homoallylic alcohols or amines or 1,4-diboronates. This reaction features a broad substrate scope with good functional group compatibility that is complementary to the existing methods for the preparation of homoallylic boronates.

A radical-induced 1,2-α-boryl migration through radical polar crossover reactions has been described. In this work, in situ formed vinyldiboron "ate" complexes from alkenyl Grignard reagent and diborylalkanes react with commercial radical precursors under light initiation. This three-component process enables diborylation of alkene. This protocol features high atom economy, a broad substrate scope as well as good functional group toleration with mild conditions.

Main observation and conclusion A method for photoinduced NaI‐promoted radical borylation of aliphatic halides and pseudohalides with bis(catecholato)diboron (B2cat2) as the boron source is introduced. The borylation reaction is operationally simple and shows high functional group tolerance and broad substrate scope. Preliminary mechanistic studies suggest that the reaction proceeds through SN2‐based radical‐generation strategy.

An ew chiral Brønsted acid, generated in situ from ac hiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This "designer acid catalyst", which is more acidic than TsOH as suggested by DFT calculations,allows the unprecedented direct asymmetric reduction of C2-aryl-substituted N-unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance.D FT calculations and mechanistic experiments indicates that this reaction undergoes C3-protonation and hydride-transfer processes.Besides,bulky C2-alkyl-substituted N-unprotected indoles are also suitable for this system.