The Evolution of Higher Order Cyanocuprates

Abstract

A personalized account of the rationales and events which led to the development of new synthetic methods based on cyanocuprate reagents is presented, highlighting the results from our laboratories over the last 10 years. 1. Introduction 2. Developing the Chemistry of R₂Cu(CN)Li₂ 3. Second Generation Reagents: R_tR_rCu(CN)Li₂ 4. Mixed Metal Reagents: R_tR_rCu(CN)LiM, M ≠ Li 5. The Transmetalation Game 5.1. 1-Alkenylstannaties 5.2. Tin Hydrides → Stannylcuprates 5.3. Cul/Bu₃SnH:Conjugate Reductions 5.4. Introduction of the Me₃Sn Group 5.5. Transmetalations of Me₃Sn-SiMe₂R: Formation of Silylcuprates 5.6. The Allylic Cuprate Story 6. Prospects of the Future 7. Final Comments: Do Higher Order Cyanocuprates Really Exist?