Base-catalyzed endo-mode cyclization of allenes: easy preparation of five- to nine-membered oxacycles

Chisato Mukai; Masaru Ohta; Haruhisa Yamashita; Shinji Kitagaki

doi:10.1021/jo0488614

Base-catalyzed endo-mode cyclization of allenes: easy preparation of five- to nine-membered oxacycles

J Org Chem. 2004 Oct 1;69(20):6867-73. doi: 10.1021/jo0488614.

Authors

Chisato Mukai¹, Masaru Ohta, Haruhisa Yamashita, Shinji Kitagaki

Affiliation

¹ Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. cmukai@kenroku.kanazawa-u.ac.jp

PMID: 15387613
DOI: 10.1021/jo0488614

Abstract

A reliable and efficient procedure for constructing five- to eight-membered oxacycles has been developed. Allenes with both a phosphoryl group and a suitable delta-hydroxyalkyl side chain at the C1-position underwent an endo mode ring-closing reaction to give five- to seven-membered oxacycles. Changing the phosphoryl group to a phosphono functionality facilitated the preparation of eight-membered congeners. Introduction of a cis double bond to the alkyl side chain of the starting allenes made possible the easy formation of medium-sized oxacycles, such as the dihydrooxocin and tetrahydrooxonin frameworks, regardless of the electron-withdrawing group (POPh2, PO(OEt)2, SOPh, and SO2Ph) at the C1-position.