Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions.

Yasuhiro Yamashita,Susumu Yoshimoto,Shū Kobayashi,Mark J Dutton

doi:10.3762/bjoc.12.140

Abstract

Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %.

Highlights

Afford the desired products in high yields with high stereoselectivities
Our group has focused on the development of metal amides as highly reactive Lewis acid/base catalysts in carbon–carbon bond-forming reactions [3]
Highly efficient asymmetric [3 + 2] cycloadditions catalyzed by chiral CuHMDS have been described

Summary

Introduction

Afford the desired products in high yields with high stereoselectivities. Based on these results, it was considered that metal amide catalysts might achieve high catalyst turnover. The reaction produced 3aa smoothly with 3 mol % catalyst loading at −40 °C, and high endo selectivity and high enantioselectivity were obtained (Table 1, entry 1).

Results

Conclusion