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Nitrogen‐Doped Carbon Enables Heterogeneous Asymmetric Insertion of Carbenoids into Amines Catalyzed by Rhodium Nanoparticles
Author(s) -
Masuda Ryusuke,
Yasukawa Tomohiro,
Yamashita Yasuhiro,
Kobayashi Shū
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202102506
Subject(s) - rhodium , catalysis , nanoparticle , chemistry , phosphoric acid , synergistic catalysis , metal , dopant , leaching (pedology) , heterogeneous catalysis , enantioselective synthesis , carbon fibers , combinatorial chemistry , organic chemistry , doping , materials science , nanotechnology , environmental science , optoelectronics , composite number , soil science , composite material , soil water
Abstract Development of stable heterogeneous catalyst systems is a crucial subject to achieve sustainable society. Though metal nanoparticles are robust species, the study of asymmetric catalysis by them has been restricted because methods to activate metal nanoparticles without causing metal leaching were limited. We developed Rh nanoparticle catalysts (NCI‐Rh) supported on nitrogen‐doped carbon as a solid ligand to interact with metals for asymmetric insertion of carbenoids into N−H bonds cocatalyzed by chiral phosphoric acid. Nitrogen dopants played a crucial role in both catalytic activity and enantioselectivity while almost no catalysis was observed with Rh nanoparticles immobilized on supports without nitrogen dopants. Various types of chiral α‐amino acid derivatives were synthesized in high yields with high enantioselectivities and NCI‐Rh could be reused in seven runs. Furthermore, we demonstrated the corresponding continuous‐flow reaction using a column packed with NCI‐Rh. The desired product was obtained efficiently for over 90 h through the reactivation of NCI‐Rh and the chiral source could be recovered.