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Published on: November 9, 2019
Asymmetric intramolecular reductive coupling of bisimines templated by chiral diborons
Tian Chen1, Hao-Yang Wang2, Ronghua Xu3
1Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University 1 Gehu Road Changzhou 213164 China jtsun@cczu.edu.cn.
Abstract:
An asymmetric intramolecular reductive coupling of bisimines has been accomplished for the first time under mild conditions with bis((+)-pinanediolato)diboron as the template, providing the unprecedented chiral dihydrophenanthrene-9,10-cis-diamines in high yields and excellent enantioselectivities. The chiral exocyclic cis-diamine products have served as effective chiral ligands for asymmetric catalysis. A DFT study highlights the crucial roles of the uncommon twisted-boat pathway (instead of the common chair type) and the steric effect in exclusively forming the cis-diamines and achieving high enantioselectivity. This reductive coupling protocol represents a significant expansion of the diboron-promoted [3,3]-sigmatropic rearrangement.
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