A photoinduced palladium-catalyzed 1,2-carbofunctionalization of conjugated dienes has been developed. This mild modular approach, which does not require employment of exogeneous photosensitizers and external oxidants, allows for efficient and highly regio- and stereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl iodides, and amines. Employment of O- and C-nucleophiles toward oxyalkylation and dialkylation products was also demonstrated. A putative π-allyl palladium radical-polar crossover path is proposed as a key event in this three-component coupling process. The utility of this protocol is highlighted by its application for derivatization of several amine-containing drugs.

The oxymetalation of terminal alkynes proceeded in a 6-endo cyclization manner with the use of indium or gallium trihalide.

The oxyindation of carbonyl-ene-yne compounds with indium trihalides proceeded efficiently to give di-, tri-, and tetrasubstituted 2-pyrones bearing a carbon–indium bond. The metalated 2-pyrone and a zwitterion intermediate were identified by X-ray crystallographic analysis. The application of organoindium compounds to oxidation or cross-coupling provided easy access to various multifunctionalized 2-pyrones. Some 2-pyrone derivatives show intense fluorescence only in the solid state (aggregation-induced emission).

Hydrofunctionalization is one of the most important transformation reactions of alkenes. Herein, we describe the development of an indium-triiodide-catalyzed hydrofunctionalization of alkenes bearing a hydroxy group using various types of organosilicon nucleophiles. Indium triiodide was the most effective catalyst, whereas typical Lewis acids such as TiCl, AlCl, and BF·OEt were ineffective. Many functional groups were successfully introduced, and these resulted in yields of 31-86%. Various styrene derivatives were also applicable to this reaction. Mechanistic investigation revealed that the present hydrofunctionalization proceeded through Brønsted acid-catalyzed intramolecular hydroalkoxylation of alkenes followed by InI-catalyzed substitution reaction of cyclic ether intermediates.