Catalytic Asymmetric 1,2-Addition of a-Isothiocyanato Phosp ho nates: Synthesis of Chiral P-Hydroxy-or β-Amiiio-Siibstituted a-Amino Phosphonic Acid Derivatives

摘要

a-Amino phosphonic acid derivatives are considered to be the most important structural analogues of a-amino acids and have a very wide range of applications. However, approaches for the catalytic asymmetric synthesis of such useful compounds are very limited. In this work, simple, efficient, and versatile organocatalytic asymmetric 1,2-addition reactions of a-isothiocyanato phosphonate were developed. Through these processes, derivatives of β-hydroxy-a-amino phosphonic acid and a,β-diamino phosphonic acid, as well as highly functionalized phosphonate-substituted spirooxindole, can be efficiently constructed (up to 99 % yield, d.r. >20:1, and >99% ee). This novel method provides a new route for the enantioselective functionalization of a-phosphonic acid derivatives.