Preparation of chiral 7,7′-disubstituted BINAPs for Rh-catalyzed 1,4-addition of arylboronic acids
摘要:
A series of new 7,7'-disubstituted BINAPs were readily prepared starting with an asymmetric catalytic oxidative coupling. They were applied as ligands to rhodium catalyzed 1,4-addition of arylboronic acids to enone,. resulting in enantioselectvities of up to 99% ee. The enantioselectivity was found to be dependent oil the size of achiral substituents. (C) 2004 Elsevier Ltd. All rights reserved.
A class of readily available optically pure 7,7′-disubstituted BINAPs for asymmetric catalysis
摘要:
A class of optically pure 7,7'-disubstituted BINAPs have been prepared starting with a catalytic asymmetric oxidative Coupling reaction. A general, concise, and straightforward synthetic procedure has been established, and is suitable for all optically pure 7,7'-disubstituted BINAPs 1a-h, regardless of the substituents' structure in the 7,7'-positions. The catalytic potential of this class of ligands has been investigated in the highly enantioselective Rh-catalyzed 1,4-addition of aryl boronic acids to enones (up to 99.8% ee), and Ru-catalyzed asymmetric hydrogenation of simple aromatic ketones (up to S/C=100,000, up to 98% ee) and beta-ketoesters (up to S/C= 10,000, up to 99.8% ee), respectively. (C) 2009 Elsevier Ltd. All rights reserved.