A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction co...A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction conditions.The reaction has a wide substrate scope and operational simplicity.Mechanistic studies suggest that1,2‐carbon migration is induced by regioselective nitrogen‐centered radical addition to the alkene unit.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
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 wit...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.展开更多
β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·...β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·HF is described.This protocol provides a general and practical approach towards a wide variety ofβ-difluorinated alkyl bromides.Bothα-andβ-bromoalkyl alkenes are suitable substrates,leading to two distinct types of products.The extension of this protocol to vinyl chloride and iodide are also feasible.The synthetic versatility of this method has been highlighted by the late-stage modification of complex small molecules and further transformations of theβ-difluorinated alkyl halides to valuable CF_(2)-containing compounds.展开更多
As a continuation of the investigation on 1,2-migration of metal carbene and free carbene, two X-ray structures of β-substituted α-diazocarbonyl compounds were obtained. The relationship between the structure and 1,...As a continuation of the investigation on 1,2-migration of metal carbene and free carbene, two X-ray structures of β-substituted α-diazocarbonyl compounds were obtained. The relationship between the structure and 1,2-migratory aptitude was discussed and an exploratory photochemical study of the diazo compounds presented.展开更多
The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single...The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21 with a = 14.3612（16） ,b = 14.7524（14） ,c = 16.898（2） ,β = 105.708（3） o,V = 3446.3（6） A^3,Mr = 1203.50,Z = 2,Dc = 1.160 Mg/m^3,μ（MoKα） = 0.90 mm^-1 and F（000） = 1296. The structure was refined to R = 0.050 and wR = 0.110 for 10213 observed reflections with I 〉 2σ（I） . The Y ion is coordinated to three phenoxo groups and three NHC ligands to form a distorted octahedral geometry. The temperature effect on the reaction leads to the 1,2-benzyl migration of NHC ligand to form the title complex.展开更多
文摘A novel nitrogen‐centered radical‐induced1,2‐carbon migration reaction of allylic alcohols has been developed.This method provides easy access to a variety ofα‐quaternary‐β‐amino ketones under mild reaction conditions.The reaction has a wide substrate scope and operational simplicity.Mechanistic studies suggest that1,2‐carbon migration is induced by regioselective nitrogen‐centered radical addition to the alkene unit.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金Financial supports from the National Natural Science Foundation of China(Nos.21772046,2193103,22001038)are gratefully acknowledged.
文摘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.
基金This work was supported by the National Natural Science Foundation of China(21961047,21901266,21971261,22022114).
文摘β-Difluorinated alkyl halides are of significant value in the modular synthesis of gem-difluorinated molecules.An exclusive 1,2-halo migratory gem-difluorination of vinyl halides with in situ-generated PhIF_(2)·HF is described.This protocol provides a general and practical approach towards a wide variety ofβ-difluorinated alkyl bromides.Bothα-andβ-bromoalkyl alkenes are suitable substrates,leading to two distinct types of products.The extension of this protocol to vinyl chloride and iodide are also feasible.The synthetic versatility of this method has been highlighted by the late-stage modification of complex small molecules and further transformations of theβ-difluorinated alkyl halides to valuable CF_(2)-containing compounds.
基金Project supported by the National Natural Science Foundation of China （Nos. 20225205, 20390050）.
文摘As a continuation of the investigation on 1,2-migration of metal carbene and free carbene, two X-ray structures of β-substituted α-diazocarbonyl compounds were obtained. The relationship between the structure and 1,2-migratory aptitude was discussed and an exploratory photochemical study of the diazo compounds presented.
基金Supported by Sichuan Application Basic Foundation (2009JY0075)
文摘The title complex L3Y（L = [O-4,6-di-tBu-C6H2-2-CH{CH（iPr2NCHCHN） }]） has been synthesized by the reaction of LiY[N（iPr） 2]4 with H2LCl and LiBu in a 1：3：2 molar ratio at 0 ℃ in THF,and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21 with a = 14.3612（16） ,b = 14.7524（14） ,c = 16.898（2） ,β = 105.708（3） o,V = 3446.3（6） A^3,Mr = 1203.50,Z = 2,Dc = 1.160 Mg/m^3,μ（MoKα） = 0.90 mm^-1 and F（000） = 1296. The structure was refined to R = 0.050 and wR = 0.110 for 10213 observed reflections with I 〉 2σ（I） . The Y ion is coordinated to three phenoxo groups and three NHC ligands to form a distorted octahedral geometry. The temperature effect on the reaction leads to the 1,2-benzyl migration of NHC ligand to form the title complex.
