Enantioselective Alkenylation of o-Carboranes via Ir-Catalyzed Asymmetric B-H Activation

Zhang, Huifang1,2; Zhang, Jie3; Qiu, Zaozao2,4; Xie, Zuowei2,3,5,6

2023-10-12

10.1021/acscatal.3c03997

ACS CATALYSIS   影响因子和分区

2155-5435

The intrinsic chirality of three-dimensional carborane derivatives is established by the substitution patterns on the icosahedral cage, which is much less studied than the planar, axial, central, and helical chirality observed in organic synthesis. Based on transition-metal-catalyzed asymmetrical B-H activation methodology, the addition of functional groups can change the symmetrical o-carborane to chiral-at-cage structures. Herein, we report an asymmetric boron vertex alkenylation of 3-acylamino-o-carboranes with diarylacetylenes for developing the cage (S)-B(4)/(R)-B(7) enantioselectivity of o-carborane. A high efficiency with up to 99% ee can be achieved in the Ir-catalyst-promoted asymmetrical (S)-B(4)-H activation under mild reaction conditions. The enantiocontrol model is suggested on the basis of DFT results where the chiral phosphine ligand plays a crucial role in this catalytic enantioselective B-H activation of o-carborane.

carborane cage chirality chiral-at-cage Ir-catalysis asymmetric B-Hbond activation alkenylation

SCI ; EI

英语

通讯

National Natural Science Foundation of China[92056106] ; Research Grants Council of HKSAR[14305420]

Chemistry

Chemistry, Physical

WOS:001092719300001

AMER CHEMICAL SOC

20234715095289

Activation analysis ; Chemical activation ; Chirality ; Enantioselectivity ; Ligands ; Phosphorus compounds ; Transition metals

Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Atomic and Molecular Physics:931.3

Web of Science

1.Henan Normal Univ, Sch Chem & Chem Engn, NMPA Key Lab Res & Evaluat Innovat Drug, Henan Key Lab Organ Funct Mol & Drug Innovat, Xinxiang 453007, Henan, Peoples R China
2.Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Hong Kong Joint Lab Chem Synth, Shanghai Inst Organ Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China
3.Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong 999077, Peoples R China
4.Univ Chinese Acad Sci, Hangzhou Inst Adv Study, Sch Chem & Mat Sci, Hangzhou 310024, Peoples R China
5.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
6.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Zhang, Huifang,Zhang, Jie,Qiu, Zaozao,et al. Enantioselective Alkenylation of o-Carboranes via Ir-Catalyzed Asymmetric B-H Activation[J]. ACS CATALYSIS,2023,13(21):13856-13862.

Zhang, Huifang,Zhang, Jie,Qiu, Zaozao,&Xie, Zuowei.(2023).Enantioselective Alkenylation of o-Carboranes via Ir-Catalyzed Asymmetric B-H Activation.ACS CATALYSIS,13(21),13856-13862.

Zhang, Huifang,et al."Enantioselective Alkenylation of o-Carboranes via Ir-Catalyzed Asymmetric B-H Activation".ACS CATALYSIS 13.21(2023):13856-13862.