Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process

Liu, Gang1; Yang, Xuanliang1; Gu, Pei2; Wang, Minyan2; Zhang, Xumu3,4; Dong, Xiu-Qin1

2024-03-06

10.1021/jacs.3c12597

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

The first earth-abundant transition metal Ni-catalyzed highly regio- and enantioselective semihydrogenation of racemic tetrasubstituted allenes via a kinetic resolution process as a challenging task was well established. This protocol furnishes expedient access to a diversity of structurally important enantioenriched tetrasubstituted allenes and chiral allylic molecules with high regio-, enantio-, and Z/E-selectivity. Remarkably, this semihydrogenation proceeded with one carbon-carbon double bond of allenes, which was regioselective complementary to the Rh-catalyzed asymmetric version. Deuterium labeling experiments and density functional theory (DFT) calculations were carried out to reveal the reasonable reaction mechanism and explain the regio-/stereoselectivity.

SCI ; IC ; CCR ; EI

英语

通讯

National Youth Talent Support Program["22071187","22271226"] ; National Natural Science Foundation of China[2022YFA1503200] ; National Key R&D Program of China["2020CFA036","2021CFA069"]

Chemistry

Chemistry, Multidisciplinary

WOS:001180746900001

AMER CHEMICAL SOC

Web of Science

1.Wuhan Univ, Coll Chem & Mol Sci, Engn Res Ctr Organosilicon Cpds & Mat, Minist Educ, Wuhan 430072, Hubei, Peoples R China
2.Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem China, Nanjing 210093, Jiangsu, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Dept Chem, Shenzhen 518000, Guangdong, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518000, Guangdong, Peoples R China

Liu, Gang,Yang, Xuanliang,Gu, Pei,et al. Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(11).

Liu, Gang,Yang, Xuanliang,Gu, Pei,Wang, Minyan,Zhang, Xumu,&Dong, Xiu-Qin.(2024).Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(11).

Liu, Gang,et al."Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.11(2024).