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Cooperative Catalysis of an Alcohol Dehydrogenase and Rhodium‐Modified Periodic Mesoporous Organosilica
Author(s) -
Himiyama Tomoki,
Waki Minoru,
Maegawa Yoshifumi,
Inagaki Shinji
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904116
Subject(s) - rhodium , chemistry , catalysis , alcohol dehydrogenase , bovine serum albumin , mesoporous material , transfer hydrogenation , mesoporous organosilica , bipyridine , alcohol , combinatorial chemistry , organic chemistry , polymer chemistry , mesoporous silica , chromatography , crystal structure , ruthenium
The combined use of a metal‐complex catalyst and an enzyme is attractive, but typically results in mutual inactivation. A rhodium (Rh) complex immobilized in a bipyridine‐based periodic mesoporous organosilica (BPy‐PMO) shows high catalytic activity during transfer hydrogenation, even in the presence of bovine serum albumin (BSA), while a homogeneous Rh complex exhibits reduced activity due to direct interaction with BSA. The use of a smaller protein or an amino acid revealed a clear size‐sieving effect of the BPy‐PMO that protected the Rh catalyst from direct interactions. A combination of Rh‐immobilized BPy‐PMO and an enzyme (horse liver alcohol dehydrogenase; HLADH) promoted sequential reactions involving the transfer hydrogenation of NAD + to give NADH followed by the asymmetric hydrogenation of 4‐phenyl‐2‐butanone with high enantioselectivity. The use of BPy‐PMO as a support for metal complexes could be applied to other systems consisting of a metal‐complex catalyst and an enzyme.