Direct Synthesis of Phosphonates and α-Amino-phosphonates from 1,3-Benzoxazines

Abstract

A straightforward and novel method for transformation of readily available 1,3-benzoxazines to secondary phosphonates and α-aminophosphonates using boron trifluoride etherate as catalyst is developed. The formation of phosphonates proceeds through ortho-quinone methide (o-QM) generated in situ, followed by a phospha-Michael addition reaction. On the other hand, the α-aminophosphonates were obtained by iminium ion formation and the subsequence nucleophilic substitution of alkylphosphites. This method can be also used for the preparation of o-hydroxybenzyl ethers through oxa-Michael addition.

Keywords

• phosphonates
• α-aminophosphonates
• o-quinone methide
• o-hydroxybenzylic ethers
• 1,3-benzoxazines