Journal of Organic Chemistry 2004-04-02

Synthesis of aromatic bisabolene natural products via palladium-catalyzed cross-couplings of organozinc reagents.

James R Vyvyan, Celeste Loitz, Ryan E Looper, Cheryl S Mattingly, Emily A Peterson, Steven T Staben

Index: J. Org. Chem. 69(7) , 2461-8, (2004)

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Abstract

Aromatic bisabolene derivatives were prepared by two methods involving cross-coupling of organozinc reagents. The first synthesis of (+/-)-glandulone A (10), as well as syntheses of (+/-)-curcuhydroquinone (8) and (+/-)-curcuquinone (9), were accomplished via coupling of a secondary alkyl zinc reagent (1,5-dimethyl-4-hexenylzinc halide, 18) to protected bromohydroquinones using Pd(dppf)Cl(2) as catalyst. Coupling of arylzinc halides with alkenyl triflate 16 using Pd(PPh(3))(4) catalyst provided a number of bisabolene derivatives and led to syntheses of dehydro-alpha-curcumene (2), (+/-)-curcuphenol (3), and (+/-)-elvirol (13). A high-yield synthesis of the (+/-)-heliannuol D precursor 29 is also reported using this method.