Domino Synthesis of Benzo-fused β,γ-Unsaturated Ketones from Alkenylboronic acids and N-Tosylhydrazone-tethered Benzonitriles

Abstract

The transition-metal-free domino reaction between alkenylboronic acids and N-tosylhydrazones from o-(2-oxoalkyl)- and o-(3-oxoalkyl)benzonitriles leads to β,γ-unsaturated indanones and tetralones featuring an α-“all-carbon” quaternary center. The employment of derivatives of α-substituted cyclopentanones and cyclohexanones led to the stereoselective preparation of β,γ-unsaturated tetrahydrocyclopenta[a]inden-8(1H)-ones, hexahydrofluorenones, and hexahydroanthracenones as cis-fused single stereoisomers. A domino sequence involving diazo compound formation/reductive alkenylation/1,3-borotropic rearrangement/intramolecular bora-aza-ene reaction is proposed to justify the formation of the products as well as the stereoselectivity.