Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Chemical Society of Japan Award for Creative Work for 2016
Catalytic Enantioselective Synthesis of Planar Chiral Cyclophanes
Ken Tanaka
Author information
JOURNALS RESTRICTED ACCESS

2018 Volume 91 Issue 2 Pages 187-194

Details
Abstract

The catalytic enantioselective synthesis of planar chiral cyclophanes has been achieved by two types of transition-metal catalysis: (1) enantioselective construction of aromatic rings by transition-metal-catalyzed [2+2+2] cycloaddition reactions; (2) enantioselective construction of ansa chains by transition-metal-catalyzed coupling reactions. The former approach has been achieved by the cationic rhodium(I)/H8-BINAP complex-catalyzed enantioselective intramolecular [2+2+2] cycloaddition of triynes, which afforded planar chiral dioxa[6]–[12]metacyclophanes with high ee values, although the yields were low. Planar chiral carba[10]–[12]paracyclophanes could also be synthesized with high yields and ee values by the cationic rhodium(I)/BDPP complex-catalyzed enantioselective intermolecular [2+2+2] cycloaddition of cyclic diynes with monoynes. On the other hand, the latter approach was achieved by the cationic rhodium(I)/BINAPHANE or palladium(II)/BINAP complex-catalyzed double C–S bond formation between dithiols and 1,4-bis(bromomethyl)benzenes, which afforded planar chiral dithia[9]–[12]paracyclophanes and dithia[3.3]paracyclophanes with varying yields and ee values.

The catalytic enantioselective synthesis of planar chiral cyclophanes has been achieved by two types of transition-metal catalysis: (1) enantioselective construction of aromatic rings by cationic rhodium(I)/chiral bisphosphine complex-catalyzed [2+2+2] cycloaddition reactions; (2) enantioselective construction of ansa chains the cationic rhodium(I) or palladium(II)/chiral bisphosphine complex-catalyzed double C–S bond forming reactions. Fullsize Image
 
Information related to the author

This article cannot obtain the latest cited-by information.

© 2018 The Chemical Society of Japan
Previous article Next article
feedback
Top