An asymmetric metal-templated route to amino acids with an isoquinolone core via a Rh(iii)-catalyzed coupling of aryl hydroxamates with chiral propargylglycine Ni(ii) complexes. Issue 47 (17th November 2022)

• Record Type: Journal Article
• Authors: Arsenov, Mikhail A.; Stoletova, Nadezhda V.; Savel'yeva, Tat'yana F.; Smol'yakov, Alexander F.; Maleev, Victor I.; Loginov, Dmitry A.; Larionov, Vladimir A.
• Is Part Of: Organic & biomolecular chemistry. Volume 20:Issue 47(2022)
• Page Start: 9385
• Page End: 9391
• Publication Date: 2022-11-17
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d2ob01970a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : The first asymmetric route to artificial amino acids with an isoquinolone skeleton was elaborated via a straightforward Rh(iii )-catalyzed C–H activation/annulation reaction. Abstract : A general protocol for the asymmetric synthesis of artificial amino acids (AAs) comprising an isoquinolone skeleton was successfully elaborated via a straightforward Rh(iii )-catalyzed C–H activation/annulation of various aryl hydroxamates with a series of robust chiral propargylglycine Ni(ii ) complexes derived from glycine (Gly), alanine (Ala) and phenylalanine (Phe) in a green solvent (methanol) under mild conditions (at room temperature under air). Notably, in the case of phenylalanine-derived complexes, the formation of unfavorable 4-substituted isoquinolone regioisomers was achieved by a catalyst control for the first time. The subsequent acidic decomposition of the obtained Ni(ii ) complexes provides the target unnatural α- and α, α-disubstituted AAs with an isoquinolone core in an enantiopure form.