Since the pioneering work on Cr(Ⅲ)-catalyzed enantioselective[4+2]/allylboration reported by Hall and co-workers,a variety of catalytic methodologies for the asymmetric allylic borylation reactions have been develope...Since the pioneering work on Cr(Ⅲ)-catalyzed enantioselective[4+2]/allylboration reported by Hall and co-workers,a variety of catalytic methodologies for the asymmetric allylic borylation reactions have been developed to provide chiral allylboronates bearing a wide range of functional groups.This review article describes recent advances in transition-metal catalyzed preparation of chiral allylboronates,especially on those in the past three years,and with the emphasis on the aspect of asymmetric catalysis.According to the mechanism of achieving the chemo-,regio-,stereo-and enantioselectivities,the discussion is divided in two parts:substrate-controlled and catalyst-controlled synthesis.展开更多
(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectivel...(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively. (S)-2 and (R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2-naphthyl bis(1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of (R)-2 or (S)-2 and some aliphetic or aromatic aldehydes in CH_ 2 Cl_ 2 at -78℃ for several hours afforded β-alkylenyl alcohols in up to 84.8% ee. Among them, optically active 1\|(3,5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared展开更多
基金NSFC(Grant No.22071095)National Young Talents Program and SUSTech for financial support.
文摘Since the pioneering work on Cr(Ⅲ)-catalyzed enantioselective[4+2]/allylboration reported by Hall and co-workers,a variety of catalytic methodologies for the asymmetric allylic borylation reactions have been developed to provide chiral allylboronates bearing a wide range of functional groups.This review article describes recent advances in transition-metal catalyzed preparation of chiral allylboronates,especially on those in the past three years,and with the emphasis on the aspect of asymmetric catalysis.According to the mechanism of achieving the chemo-,regio-,stereo-and enantioselectivities,the discussion is divided in two parts:substrate-controlled and catalyst-controlled synthesis.
文摘(R)- and (S)-2-Allyl-1,3,2-dinaphtho(α,β)\dioxaborepin ((R)-2 and (S)-2) have been first prepared by the reaction of (R)-(+)- or (S)-(-)-1,1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively. (S)-2 and (R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2-naphthyl bis(1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of (R)-2 or (S)-2 and some aliphetic or aromatic aldehydes in CH_ 2 Cl_ 2 at -78℃ for several hours afforded β-alkylenyl alcohols in up to 84.8% ee. Among them, optically active 1\|(3,5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared
