General Access to Modified α‐Amino Acids by Bioinspired Stereoselective γ‐C−H Bond Lactonization. Issue 9 (23rd December 2020)

• Record Type: Journal Article
• Authors: Vicens, Laia; Bietti, Massimo; Costas, Miquel
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 9(2021)
• Page Start: 4740
• Page End: 4746
• Publication Date: 2020-12-23
• Subjects: amino acids -- C−H oxidation -- HAT -- hydrogen peroxide -- stereoselectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202007899
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: α‐Amino acids represent a valuable class of natural products employed as building blocks in biological and chemical synthesis. Because of the limited number of natural amino acids available, and of their widespread application in proteomics, diagnosis, drug delivery and catalysis, there is an increasing demand for the development of procedures for the preparation of modified analogues. Herein, we show that the use of bioinspired manganese catalysts and H2 O2 under mild conditions, provides access to modified α‐amino acids via γ‐C−H bond lactonization. The system can efficiently target 1°, 2° and 3° γ‐C−H bonds of α‐substituted and achiral α, α‐disubstituted α‐amino acids with outstanding site‐selectivity, good to excellent diastereoselectivity and (where applicable) enantioselectivity. This methodology may be considered alternative to well‐established organometallic procedures. Abstract : Bioinspired stereoselective γ‐aliphatic C−H bond lactonization of α‐amino acids using a manganese catalyst and H2 O2 is reported. This method allows the oxidation of 1°, 2° and 3° C−H bonds and the enantioselective preparation of chiral α, α‐disubstituted‐α‐amino acid derivatives.