One‐Pot Generation of Bicyclo[3.1.0]hexanols and Cyclohexanones by Double Interrupted Nazarov Reactions

Organoaluminum‐mediated double interrupted Nazarov cyclization to access bicyclo[3.1.0]hexanols via nucleophilic methyl attack followed by Simmons–Smith‐type electrophilic cyclopropanation is reported. These alcohols can undergo ring opening to afford cyclohexanones or cyclohexenones, broadening the range of scaffolds available via interrupted Nazarov reaction beyond the usual cyclopentanoid products. Throughout the sequence, a total of four new C−C bonds are formed, along with four new stereogenic centers. Nazarov meets Simmons–Smith: AlMe3 has three roles—dienone Lewis acid activation, nucleophilic methyl transfer, and Simmons–Smith cyclopropanation, furnishing bicyclo[3.1.0]‐hexanols that can undergo subsequent reorganization.