Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.
J Am Chem Soc
; 136(23): 8209-12, 2014 Jun 11.
Article
em En
| MEDLINE
| ID: mdl-24856045
ABSTRACT
Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Compostos Bicíclicos com Pontes
/
Hidrocarbonetos Acíclicos
Idioma:
En
Ano de publicação:
2014
Tipo de documento:
Article