All-Carbon [3+3] Oxidative Annulations of 1,3-Enynes by Rhodium(III)-Catalyzed C-H Functionalization and 1,4-Migration.

1,3-Enynes containing allylic hydrogens cis to the alkyne function as three-carbon components in rhodium(III)-catalyzed, all-carbon [3+3] oxidative annulations to produce spirodialins. The proposed mechanism of these reactions involves the alkenyl-to-allyl 1,4-rhodium(III) migration.

Synthesis of benzopyrans by Pd(II)- or Ru(II)-catalyzed C-H alkenylation of 2-aryl-3-hydroxy-2-cyclohexenones.

2-Aryl-3-hydroxy-2-cyclohexenones are shown to be competent substrates for palladium- and ruthenium-catalyzed C-H alkenylation reactions with terminal alkenes, providing, in most cases, benzopyrans.

Enantioselective Rh(I)-catalyzed cyclization of arylboron compounds onto ketones.

Rhodium complexes based upon chiral sulfinamide-alkene, TADDOL-derived phosphoramidite, or diene ligands catalyze cyclizations of arylboron compounds onto ketones, generating a variety of products containing five-, six-, or seven-membered rings with good yields and high enantioselectivities.