Fig. 3: Scope of the catalytic asymmetric Wagner–Meerwein shift.

Reactions were performed at 0.25 mmol scale. Isolated yields after chromatographic purification. The enantiomeric ratio was determined by gas chromatography analysis (Supplementary Information has details). ^aAt 50 °C for 24 h. ^bWith catalyst 2f in n-hexane at room temperature for 36 h. ^cWith catalyst 2g in methyl cyclohexane at 60 °C for 48 h. ^dWith catalyst 2g in methyl cyclohexane at 60 °C for 72 h. ^eWith catalyst 2g in methyl cyclohexane at 80 °C for 96 h. ^fWith catalyst 2g in methyl cyclohexane at 90 °C for 6 days. ^gWith catalyst 2d in methyl cyclohexane at 50 °C for 24 h. The structure of osmate ester 7 derived from product 3g, H atoms and the disordered atoms are omitted for clarity. The structure of one of the two independent molecules of osmate ester 8 contained in the unit cell derived from product 3n and H atoms are omitted for clarity. The structure of osmate ester 9 derived from product 3o, H atoms, water molecule and the disordered atoms are omitted for clarity (Supplementary Figs. 10–16). Bn, benzyl; TFA, trifluoroacetic acid; TMEDA, N,N,N′,N′-tetramethylethylenediamine.