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Gold(I)‐Catalyzed Asymmetric Desymmetrization of meso‐ Alkynyl Diols and Kinetic Resolution of the Corresponding dl ‐Diols: Effects of Celite Filtration and Silver Salts
Author(s) -
Sota Yumi,
Yamamoto Masaaki,
Murai Masato,
Uenishi Jun'ichi,
Uemura Motokazu
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405889
Subject(s) - desymmetrization , kinetic resolution , chemistry , catalysis , reactivity (psychology) , selectivity , salt (chemistry) , diol , organic chemistry , medicinal chemistry , enantioselective synthesis , medicine , alternative medicine , pathology
The asymmetric desymmetrization of meso‐ 2‐alkynylbenzenediols through the use of a combination of axially chiral diphosphine(AuCl) 2 precatalysts and silver salt co‐catalysts gave optically active isochromene compounds with high enantioselectivities in good yields. The corresponding dl ‐diol isomers underwent efficient kinetic resolution to give the cyclized isochromenes and recovered diols with high enantioselectivities under similar conditions. The high reactivity and selectivity in the desymmetrization of the meso ‐diols is independent of the combination of axially chiral diphosphine(AuCl) 2 precatalyst and silver salt co‐catalyst, whereas the corresponding tricarbonylchromium complexes of alkynylbenzenediols were affected by the combination of the diphosphine(AuCl) 2 and silver salt. The reactivity was largely dependent on the nature of the gold(I) species.