钌催化双环烯烃与炔基膦酸酯的[2 + 2]环加成反应。

Ruthenium-catalyzed [2 + 2] cycloadditions of bicyclic alkenes with alkynyl phosphonates.

作者信息

Cockburn Neil, Karimi Elham, Tam William

机构信息

Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1, Canada.

出版信息

J Org Chem. 2009 Aug 7;74(15):5762-5. doi: 10.1021/jo9010206.

DOI:10.1021/jo9010206

PMID:19572573

Abstract

Ruthenium-catalyzed [2 + 2] cycloadditions of bicyclic alkenes with alkynyl phosphonates were investigated. The phosphonate moieties were found to be compatible with the Ru-catalyzed cycloadditions giving the corresponding cyclobutene cycloadducts in low to excellent yield (up to 96%). Alkynyl phosphonates showed lower reactivity than other heteroatom-substituted alkynes such as alkynyl halides, ynamides, alkynyl sulfides, and alkynyl sulfones and required a higher reaction temperature and much longer reaction time.

摘要

研究了钌催化的双环烯烃与炔基膦酸酯的[2 + 2]环加成反应。发现膦酸酯部分与钌催化的环加成反应相容，能以低至优异的产率（高达96%）得到相应的环丁烯环加成产物。炔基膦酸酯的反应活性低于其他杂原子取代的炔烃，如炔基卤化物、烯炔酰胺、炔基硫醚和炔基砜，需要更高的反应温度和更长的反应时间。