Perfectly “Anti-Apicophilic” Phosphoranes: Conversion of a 1-Hydro-5-carbaphosphatrane into 1-Alkyl- and 1-Aryl-5-carbaphosphatranes

Abstract

1-Alkyl- and 1-aryl-5-carbaphosphatranes were prepared by the reaction of 1-hydro-5-carbaphosphatrane with nucleophiles and subsequent intramolecular oxidative cyclization. X-ray crystallographic investigation of the t-butyl derivative revealed that it has a perfectly “anti-apicophilic” arrangement. The apical ¹ J _PC coupling constants of the 5-carbaphosphatranes were extraordinarily large.

Keywords:

• Apicophilicity
• carbaphosphatrane
• coupling constant
• trigonal bipyramidal structure

Dedicated to Professor Marian Mikołajczyk from the CBMiM PAN in Łódź, Poland, on the occasion of his 70th birthday.

This study was supported by the Grants-in-Aid for The Global COE Program for Chemistry Innovation (T.K.) and for Scientific Research (T.K.) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. We thank Tosoh Finechem Corporation for the generous gifts of alkyllithiums.