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.

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.

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. -In the presence of appropriate chiral Rh catalysts, boron compounds of type (I), (V), (VII), and (IX) undergo cyclization to afford isoquinoline, dibenzoazepine, fluorene, or benzofuran derivatives with high enantioselectivity. -(LOW, D. W.; PATTISON, G.; WIECZYSTY, M. D.; CHURCHILL, G. H.; LAM*, H. W.; Org. Lett. 14 (2012) 10, 2548-2551, http://dx.doi.org/10.1021/ol300845q ; EaStChem, Sch. Chem., Univ. Edinburgh, Edinburgh EH9 3JJ, UK; Eng.) -Jannicke 38-028