The direct electrophilic, nucleophilic, and amphiphilic allylations of allylic alcohol by use of a palladium catalyst and organometallic reagents such as organoborane and organozinc has been developed. The phosphine-borane compound works as the effective ligand for palladium-catalyzed direct allylic amination of allylic alcohol. Thus, with secondary amines, the reaction was completed in only 1 h, even at room temperature.

Tandem reaction: The Pd-catalyzed three-component coupling reaction of an allylic alcohol, terminal alkyne, and organoborane to give (E)-1-substituted 2-alkyl-1,4-pentadienes, involving geminal allylation and alkylation at the acetylenic terminal carbon, is described. Bis-diene undergoes a similar multicomponent coupling reaction with acetylene and organoborane, involving cyclization of bis-π-allylpalladium, to form trans-allyl pentadienyl cyclic and heterocyclic compounds with excellent regio- and stereoselectivities (see scheme).

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Palladium-Catalyzed Tandem Coupling Reaction of Alkyne, Conjugated Diene, and Triethylborane. -(TAKUSHIMA, D.; FUKUSHIMA, M.; SATOMURA, H.; ONODERA, G.; KIMURA*, M.; Heterocycles 86 (2012) 1, 171-180, http://dx.doi.org/10.3987/com-12-s(n)70 ; Grad. Sch. Eng., Nagasaki Univ., Nagasaki 852, Japan; Eng.) -R. Langenstrassen 18-045

The palladium‐catalyzed three‐component coupling reaction of allylic alcohols, terminal alkynes, and organoboranes preferentially gives (E)‐substituted alkylpentadienes, involving geminal allylation and alkylation at the acetylenic terminal carbon.