Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons

Zhou，Mingkang1; Lin，Yaodong1; Chen，Xiao Xuan3; Xu，Guangqing1; Chung，Lung Wa3; Tang，Wenjun1,2

2023-04-17

10.1002/anie.202300334

Angewandte Chemie - International Edition   Impact Factor & Quartile

1433-7851

1521-3773

We herein describe the chiral diboron-templated asymmetric homocoupling of aryl alkyl ketimines, providing for the first time a series of chiral vicinal tetrasubstituted diamines with excellent ee values and good to high yields. The powerful and efficient diboron-participated [3,3]-sigmatropic rearrangement is successfully demonstrated by the homocoupling of a variety of ketimines thanks to the rational design and engineering of chiral diborons. Systematic DFT studies suggest that two chiral diborons adopt different conformational assembling strategies to couple the diboron template with ketimine substrates in their tight concerted transition states to ensure the excellent enantioselectivities. The synthetic value of chiral vicinal tetrasubstituted diamines is demonstrated by the asymmetric α-bromination of aliphatic aldehydes by employing a chiral vicinal tetrasubstituted diamine-based organocatalyst.

Asymmetric Homocoupling Asymmetric α-Bromination Chiral Diborons Chiral Tetrasubstituted Diamines Halogen Bonding

SCI

English

NI Journal Papers

Corresponding

National Key Research and Development Program of China[2021YFF0701601];National Key Research and Development Program of China[2022YFA1503702];National Natural Science Foundation of China[21432007];National Natural Science Foundation of China[21572246];National Natural Science Foundation of China[21702223];National Natural Science Foundation of China[21725205];National Natural Science Foundation of China[21933003];National Natural Science Foundation of China[22071261];National Natural Science Foundation of China[22193020];National Natural Science Foundation of China[22193023];National Natural Science Foundation of China[82188101];

WOS:000953333400001

CHEMISTRY

2-s2.0-85150029255

Scopus

1.State Key Laboratory of Bio-Organic and Natural Products Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Shanghai,345 Ling Ling Road,200032,China
2.School of Chemistry and Materials Science,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,Hangzhou,1 Sub-lane Xiangshan,310024,China
3.Shenzhen Grubbs Institute,Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518055,China

Zhou，Mingkang,Lin，Yaodong,Chen，Xiao Xuan,et al. Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons[J]. Angewandte Chemie - International Edition,2023,62(17).

Zhou，Mingkang,Lin，Yaodong,Chen，Xiao Xuan,Xu，Guangqing,Chung，Lung Wa,&Tang，Wenjun.(2023).Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons.Angewandte Chemie - International Edition,62(17).

Zhou，Mingkang,et al."Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons".Angewandte Chemie - International Edition 62.17(2023).