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Chloride‐Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins
Author(s) -
Kita Yusuke,
Hida Shoji,
Higashihara Kenya,
Jena Himanshu Sekhar,
Higashida Kosuke,
Mashima Kazushi
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601748
Subject(s) - rhodium , asymmetric hydrogenation , chemistry , catalysis , allylic rearrangement , enantioselective synthesis , medicinal chemistry , chloride , organic chemistry
Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride‐bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)] 2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of ( E )‐prop‐1‐ene‐1,2‐diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems.