Enantioselective synthesis of C-2-symmetric dimethyl cyclohexadiene-dicarboxylates through cationic rhodium(I)/modified-BINAP-catalyzed [2+2+2] cycloadditions

A cationic rhodium(I)/(S)-Tol-BINAP complex was employed to catalyze an enantioselective intramolecular [2+2+2] cycloaddition of a trans enediyne leading to a C-2-symmetric tricyclic dimethyl cyclohexadienedicarboxylate in 95% yield with 59% ee. A cationic rhodium(I)/(R)-H-8-BINAP complex was employ...

Full description

Saved in:
Bibliographic Details
Published inSynlett no. 9; pp. 1426 - 1430
Main Authors Tanaka, Ken, Nishida, Goushi, Sagae, Hiromi, Hirano, Masao
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 01.06.2007
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
cyclohexadienes
cycloadditions
asymmetric catalysis
ALKYNES
BINAP
AXIALLY CHIRAL BIARYLS
CONSTRUCTION
1,6-DIYNES
DOUBLE-BOND
CYCLIZATION
rhodium
REGIOSELECTIVE INTERMOLECULAR CYCLOTRIMERIZATION
ENYNES
Online AccessGet more information

Cover

More Information
Summary:A cationic rhodium(I)/(S)-Tol-BINAP complex was employed to catalyze an enantioselective intramolecular [2+2+2] cycloaddition of a trans enediyne leading to a C-2-symmetric tricyclic dimethyl cyclohexadienedicarboxylate in 95% yield with 59% ee. A cationic rhodium(I)/(R)-H-8-BINAP complex was employed to catalyze an intermolecular [2+2+2] cycloaddition of 1,6-diynes with dimethyl fumarate leading to C2-symmetric bicyclic dimethyl cyclohexadienedicarboxylates in 35-96% yields with ee values of 82-98%.
ISSN:0936-5214
1437-2096
DOI:10.1055/s-2007-980372