TRANSITION-METAL-CATALYZED, CHLORINE-TRANSFER RADICAL CYCLIZATIONS OF2-(3-ALKEN-1-OXY)-2-CHLOROACETATES - FORMAL TOTAL SYNTHESIS OF AVENACIOLIDE AND ISOAVENACIOLIDE

Authors
UDDING JH TUIJP KCJM VANZANDEN MNA HIEMSTRA H SPECKAMP WN
Citation
Jh. Udding et al., TRANSITION-METAL-CATALYZED, CHLORINE-TRANSFER RADICAL CYCLIZATIONS OF2-(3-ALKEN-1-OXY)-2-CHLOROACETATES - FORMAL TOTAL SYNTHESIS OF AVENACIOLIDE AND ISOAVENACIOLIDE, Journal of organic chemistry, 59(8), 1994, pp. 1993-2003
Citations number
56
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
Journal of organic chemistry → ACNP
ISSN journal
00223263
Volume
59
Issue
8
Year of publication
1994
Pages
1993 - 2003
Database
ISI
SICI code
0022-3263(1994)59:8<1993:TCRCO>2.0.ZU;2-2
Abstract
A novel method for the synthesis of functionalized tetrahydrofurans is described. This method involves the treatment of 2-(3-alken-1-oxy)-2- chloroacetates 1 with a catalytic amount of Cu(bpy)Cl in refluxing 1,2 -dichloroethane to give good yields of 3-(1-chloroalkyl)-2-tetrahydrof uran carboxylic esters 2. The stereochemical course of the radical cyc lizations shows a-preference for the formation of 2,3-cis-substituted tetrahydrofurans in all cases. This selectivity is exploited in the fo rmation of bicyclic lactones which form spontaneously upon ester hydro lysis. As an application of this methodology a formal total synthesis of avenaciolide (28) and isoavenaciolide (29) is described.