Copper-Catalyzed Aminothiolation of 1,3-Dienes via a Dihydrothiazine Intermediate.
Angew Chem Int Ed Engl
; 56(20): 5536-5540, 2017 05 08.
Article
em En
| MEDLINE
| ID: mdl-28407352
ABSTRACT
Heteroatom-containing organic molecules are of particular interest to medicinal chemists and materials scientists. A strategy to reach these architectures via direct difunctionalization of abundant 1,3-dienes is especially attractive. Herein, we describe the development of a regio- and diastereoselective 1,4-aminothiolation of 1,3-dienes with a sulfur diimide reagent, a copper catalyst, and alkyl Grignard reagents. This unique protocol provides remote nitrogen and sulfur functionalities with high levels of stereocontrol. The reaction proceeds via a tandem hetero-Diels-Alder cycloaddition of N,N'-bis(benzenesulfonyl)sulfur diimide with 1,3-diene followed by copper-catalyzed Grignard substitution. Mechanistic studies support a copper catalyzed formation of an unprecedented [10-S-4] sulfurane that reductively eliminates to afford a 3,6-dihydrothiazine, which is selectively converted to 1,4-aminothiols.
Palavras-chave
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Compostos de Sulfidrila
/
Tiazinas
/
Cobre
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2017
Tipo de documento:
Article
País de afiliação:
Estados Unidos