Skeletal Migrations Observed during the Cob(I)alamin-Catalyzed Reduction of 4β-(tert-Butyl)-1β-(1-methylvinyl)cyclohexanecarbaldehyde

During the cob(I)alamin(1(I))‐catalyzed reduction of 3, intermediate formation of 2 and final generation of 4–10 was observed (see Scheme 1, cf. Tables 1 and 2). Identical products in similar ratios were generated starting from either 2 or 3. Accepting the intermediate formation of six interconnected cobalt complexes, i.e. A–F (cf. Scheme 2), the generation of all the products observed can be explained.