Rhodium(I)-Catalyzed Asymmetric Alkyl Carbene B-H Bond Insertion: Enantioselective Synthesis of Versatile Chiral Alkylboranes

被引:0
|
作者
Liu, Jian-Guo [1 ,2 ]
Liu, Bo [1 ,2 ]
Li, Ziyan [1 ,2 ]
Xu, Ming-Hua [1 ,2 ,3 ]
机构
[1] Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
[2] Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
[3] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Henan, Peoples R China
来源
CCS CHEMISTRY | 2024年
基金
中国国家自然科学基金;
关键词
metal carbene; B-H bond insertion; chiral diene; rhodium(I); alkylborane; CONJUGATE ADDITIONS; CARBONYL-COMPOUNDS; EFFICIENT ROUTE; BORYLATION; SECONDARY; ESTERS; HYDROBORATION; CATALYST; KETONES;
D O I
10.31635/ccschem.024.202404591
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Recent advances in transition metal-asymmetric carbene B-H insertion reactions provide a straightforward and powerful protocol to access chiral organoboron compounds. However, the related reaction involving linear alkyl carbenes has not been successfully developed. Apart from the difficulty of controlling the enantioselectivity, another major challenge is the high propensity of the alkyl metal carbene to undergo a beta-hydride migration to form undesired alkenes. Herein, we report our development of an efficient alkyl carbene B-H insertion reaction using rhodium(I)/diene complexes as the catalysts. This simple catalytic system not only reduces the formation of alkene byproduct but also achieves high enantioselectivity of the carbene B-H insertion. This method facilitates easy asymmetric access to a wide variety of structurally diverse alkylboranes in high yields, and their further synthetic application and transformation have also been described. Mechanistic studies show that the beta-hydride migration is less favorable than the carbene insertion pathway under the rhodium(I)/diene catalytic system and that the B-H bond insertion is the rate-limiting step. [GRAPHICS]
引用
收藏
页数:12
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