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Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]‐Hydrogenase
Author(s) -
Pan HuiJie,
Hu Xile
Publication year - 2020
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.201914377
Subject(s) - hydrogenase , hydride , catalysis , transfer hydrogenation , manganese , chemistry , combinatorial chemistry , substrate (aquarium) , active site , asymmetric hydrogenation , hydrogen , photochemistry , organic chemistry , enantioselective synthesis , biology , ecology , ruthenium
Abstract [Fe]‐hydrogenase is an efficient biological hydrogenation catalyst. Despite intense research, Fe complexes mimicking the active site of [Fe]‐hydrogenase have not achieved turnovers in hydrogenation reactions. Herein, we describe the design and development of a manganese(I) mimic of [Fe]‐hydrogenase. This complex exhibits the highest activity and broadest scope in catalytic hydrogenation among known mimics. Thanks to its biomimetic nature, the complex exhibits unique activity in the hydrogenation of compounds analogous to methenyl‐H 4 MPT + , the natural substrate of [Fe]‐hydrogenase. This activity enables asymmetric relay hydrogenation of benzoxazinones and benzoxazines, involving the hydrogenation of a chiral hydride transfer agent using our catalyst coupled to Lewis acid‐catalyzed hydride transfer from this agent to the substrates.