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.

Osmium-mediated oxidative cyclizations: a study into the range of initiators that facilitate cyclization.

A general route to prepare substituted, saturated five-membered heterocycles has been developed. The application of a wide range of starting materials to the osmium-catalyzed oxidative cyclization reaction is described. Diols, hydroxy-amides, hydroxy-sulfonamides, and carbamates all cyclize in moderate to excellent yields to give cis-tetrahydrofurans and pyrrolidines, depending upon the position of the heteroatoms in the starting materials.

Approaches to the quaternary stereocentre and to the heterocyclic core in diazonamide A using the Heck reaction and related coupling reactions.

In model studies towards the quaternary centre at the heart of diazonamide A (early structure 2; revised structure 1), cyclisations of the alkene-substituted iodoaryls 4, 13, 18 and 23, under Heck reaction conditions, were shown to lead to the corresponding benzodihydrofuran 5, benzofuranone 14 and the oxindoles 19 and 24 respectively, in 50-80% yield. Further manipulation of the benzodihydrofuran 5 then led to the intermediates 30, 33 and 39, which make up parts of the oxazole-indole heterocyclic core in diazonamide A. Attempts to perform a corresponding 13-exo-trig Heck cyclisation from the precursor 46a, prepared from 44 and 45, leading to 47 were not successful.