Regiodivergent Synthesis of Butenolide-Based α- and β-Amino Acid Derivatives via Base-Controlled Azirine Ring Expansion

Pavel A Sakharov; Nikolai V Rostovskii; Alexander F Khlebnikov; Mikhail S Novikov

doi:10.1021/acs.orglett.0c00793

Regiodivergent Synthesis of Butenolide-Based α- and β-Amino Acid Derivatives via Base-Controlled Azirine Ring Expansion

Org Lett. 2020 Apr 17;22(8):3023-3027. doi: 10.1021/acs.orglett.0c00793. Epub 2020 Mar 31.

Authors

Pavel A Sakharov¹, Nikolai V Rostovskii¹, Alexander F Khlebnikov¹, Mikhail S Novikov¹

Affiliation

¹ St. Petersburg State University, Institute of Chemistry, 7/9 Universitetskaya nab., St. Petersburg 199034, Russia.

PMID: 32227960
DOI: 10.1021/acs.orglett.0c00793

Abstract

A method for the preparation of 5-aminobutenolides from 2-bromo-2H-azirine-2-carboxylic esters/amides with arylacetic acids has been developed. The reaction regioselectivity can be switched by a change of the basic catalyst, making it possible to prepare both butenolide-based α- and β-amino acid derivatives. The change in the regioselectivity is interpreted in terms of the stability and reactivity of the enolates formed during the S_N2' substitution of the bromine in the azirine by the carboxylate ion.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

4-Butyrolactone / analogs & derivatives*
4-Butyrolactone / chemical synthesis
4-Butyrolactone / chemistry
Amides / chemistry
Amino Acids / chemical synthesis*
Amino Acids / chemistry
Azirines / chemistry*
Esters / chemistry
Molecular Structure
Stereoisomerism

Substances

Amides
Amino Acids
Azirines
Esters
butenolide
4-Butyrolactone