期刊
CHEM
卷 7, 期 6, 页码 1588-1601出版社
CELL PRESS
DOI: 10.1016/j.chempr.2021.03.002
关键词
-
资金
- NSF [CHE-1900375]
- NIH [R01-GM102554]
A catalytic radical process for asymmetric cyclopropanation using Co(II)-based metalloradical catalysis has been developed, enabling the stereoselective synthesis of chiral cyclopropyl alpha-amino acid derivatives with high yields, excellent enantioselectivities, and (Z)-diastereoselectivity. Computational and experimental studies support a stepwise radical mechanism for the reaction, showcasing potential applications in the synthesis of dipeptides.
A catalytic radical process has been developed for asymmetric cyclopropanation of dehydroaminocarboxylates with in situ-generated a-aryldiazomethanes via Co(II)-based metalloradical catalysis (MRC). Through fine-tuning the environments of D-2-symmetric chiral amido-porphyrin platform as the supporting ligands, the Co(II)-metalloradical system can effectively activate various alpha-aryldiazomethanes to cyclo-propanate different dehydroaminocarboxylates undermild conditions, enabling the stereoselective synthesis of chiral cyclopropyl alpha-amino acid derivatives. In addition to high yields and excellent enantioselectivities, the Co(II)-catalyzed asymmetric radical cyclopropanation exhibits (Z)-diastereoselectivity, which is the opposite of uncatalyzed thermal reaction. Combined computational and experimental studies support a stepwise radicalmechanism for the Co(II)-catalyzed cyclopropanation reaction. The resulting enantioenriched (Z)-alpha-amino-beta-arylcyclopropanecarboxylates, as showcased for the efficient synthesis of dipeptides, may serve as unique non-proteinogenic amino acid building blocks for the design and preparation of novel peptides with restricted conformations.
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