Catalytic Asymmetric 1,2-Addition of α-Isothiocyanato Phosphonates: Synthesis of Chiral β-Hydroxy- or β-Amino-Substituted α-Amino Phosphonic Acid Derivatives

-Amino phosphonic acid derivatives are considered to be the most important structural analogues of -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 -isothiocyanato phosphonate were developed. Through these processes, derivatives of -hydroxy--amino phosphonic acid and ,-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 -phosphonic acid derivatives.