Recent Advances in Halogen–Metal Exchange Reactions

Abstract

A fast Br/La exchange was conducted to generate cyclometalated lanthanum intermediates leading to the facile preparation of a series of functionalized compounds, which demonstrated the powerful utility of this new halogen−metal exchange in organic synthesis.

Access to Valuable Chalcogen-Containing Biaryl Derivatives via Regioselective 2,2′-Dichalcogenation of 2-Bromobiaryls

“…Lanthanum is abundant in the earth’s crust and nontoxic to humans compared to transition metals, making itself a valuable element in the development of sustainable chemistry. In our previous work, we have prepared the organolanthanum reagent n Bu 2 LaCl·4LiCl enabling the cyclolanthanation of 2-bromobiaryls ( 1 ) via sequential Br/La-exchange and C–H lanthanation, leading to the in situ generation of cyclolanthanated reagents with versatile reactivities . Herein, we develop an organolanthanum-mediated regioselective 2,2′-dichalcogenation of 2-bromobiaryls by combining the cyclolanthanation reaction with the electrophilic chalcogenation reaction using a one-pot two-step procedure (Scheme C).…”