Bicyclo[3.2.0]heptane-Based Enamides by Ru/PNNP-Catalyzed Enantioselective Ficini Reactions: Scope and Application in Ligand Design

Abstract

Double chloride abstraction from [RuCl₂(PNNP)] [PNNP­ = (S,S)-N,N′-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine] gives the elusive dicationic adduct [Ru(OEt)₂(PNNP)]^²+ which catalyzes the [2+2] cycloaddition of cyclic alkylidene β-keto esters with a variety of ynamides to produce bicyclo[3.2.0]heptane-based enamides with high yields and enan­tioselectivity. The structural features of these products are discussed and selected examples are converted into highly modular diene, phosphite-alkene, and diphosphite derivatives, which were tested as bidentate ligands with Rh(I), Ir(I), and Pd(II).

asymmetric catalysis - biaryls - cycloaddition - bicyclic compounds - ligands - phosphorus - ruthenium

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