The synthesis of (-)-hamigeran B has been achieved, based on a new approach to cyclopentane construction, the rhodium-mediated intramolecular C-H insertion of α-aryl-α-diazo ketones. The endo isopropyl group was installed by selective hydrogenation of a cyclopropylidene substituent.

Two complementary procedures have been developed for the conversion of the oximes of alpha-aryl ketones to azirines. On heating, the azirines rearrange smoothly to the corresponding indoles. The overall transformation offers a versatile route to indoles, complementary to the Fischer indole synthesis.

Some long chain α-aryl α-diazo ketones under Rh catalysis cyclize efficiently to the corresponding cyclohexanones. This is in marked contrast to the cyclizations of α-diazo β-ketoesters, which consistently deliver cyclopentanone products.

A synthetic route to the carboline disaccharide domain (2) of shishijimicin A (1) has been developed. The convergent synthesis relies on a novel application of the Reetz–Müller-Starke reaction to form the central, sulfur-bearing quaternary carbon center and addition of the carboline structural motif as a dianion to a disaccharide aldehyde fragment.

Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones.