Iridium-Catalyzed Enantioconvergent Allylation of a Boron-Stabilized Organozinc Reagent

Abstract

An iridium-catalyzed enantioconvergent coupling of the versatile boron-stabilized organozinc reagent BpinCH2ZnI with a racemic branched allylic carbonate has been developed here, which differs from our previous work by using 1,1-bisborylmethane through the kinetic resolution process. The reaction has a broad substrate scope, and various chiral homoallylic organoboronic esters could be obtained in good yields with excellent enantioselectivities. The synthetic practicability of the products was demonstrated by their conversion to other useful families of compounds.

Enantioselective [2,3]-Wittig Rearrangement of Carboxylic Acid Derived Enolates by Tetradentate Chiral Lithium Amide

“…The absolute configuration was determined as (2S,3R) by specific rotation of the derivative illustrated below (lit 11 [α]D 20 = +67.5 (c = 0.545, CHCl3, 3S), lit 12 [α]D 20 = −36.0 (c = 0.25, CHCl3, 94%ee, 3R), lit 13 [α]D 20 = −33.0 (c = 0.23, CHCl3, 95%ee, 3R), lit 14 [α]D 20 = −59.8 (c = 1, CHCl3, >99%ee, 3R)).…”

Recent advances in iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands

“…Zhan reported Ir-catalyzed enantioselective allylic alkylation with boron-stabilized organozinc reagent. 41 Ester 3 reacted with α-borylorganozinc reagents (PinBCH 2 ZnI) to give homoallylboronates with high enantioselectivities.…”

Theoretical Study on the Mechanism of Cobalt-Catalyzed C–O Silylation and Stannylation

“…Therefore, the synthesis of compounds containing C–Si and C–Sn bonds by experimental means has aroused chemists’ thinking. As many contributions have reported, transition metal-catalyzed (TMC) cross-coupling is a powerful toolbox for manipulating C–X (X = heteroatom) bonds in the synthesis of agricultural chemicals, pharmaceuticals, and raw commodity chemicals. − Consequently, TMC could also be a potential tool for the construction of C–Si and C–Sn bonds …”