Zn-Catalyzed Asymmetric Allylation for the Synthesis of Optically Active Allylglycine Derivatives. Regio- and Stereoselective Formal α-Addition of Allylboronates to Hydrazono Esters

We have developed Zn-catalyzed asymmetric allylation of hydrazono esters with allylboronates. The reactions proceeded smoothly in high yields and high stereoselectivities. Remarkably, formal α-addition occurred for α-substituted allylboronates exclusively, and excellent stereoselectivities were observed. This is the first example of catalytic regio- and stereoselective allylations with formal α-addition. In addition, the reaction proceeded in aqueous media, and the use of water is essential. Zn(OH) 2 might be a catalyst in this asymmetric allylation, and the catalytic activity of Zn(OH) 2 was confirmed. This is also the first case of chiral metal hydroxide-catalyzed asymmetric reactions.