Nickel-catalyzed acylstannylation and alkynylstannylation of 1,2-dienes

作者：Nakao Y; Shirakawa E^*; Tsuchimoto T; Hiyama T

来源：Journal of Organometallic Chemistry, 2004, 689(23): 3701-3721.

DOI：10.1016/j.jorganchem.2004.07.037

• nickel
• carbometalation
• 1,2-diene
• acylstanane
• alkynylstannane

Carbostannylation of 1,2-dienes using acyl- and alkynylstannanes was achieved by means of nickel catalysis. In particular, acylstannylation of 1,2-dienes could be carried out with bis(1,5-cyclooctadiene)nickel [Ni(cod)(2)] and acylstannanes to give selectively alpha-acylmethyl(vinyl)stannanes. The reaction was also applicable to acylstannanes prepared in situ by protonolysis of alpha-alkoxyalkenylstannanes or by reactions of alpha-silyloxyvinylstannanes with aldehyde acetals. For alkynylstannylation, a combination of Ni(cod)(2) and 1,3-bis(diphenylphosphino)propane (dppp) was found to be effective to afford alpha-alkynylmethyl(vinyl)stannanes, whereas the Ni(cod)(2)-1,3-bis(dimethylphosphino)propane (dmpp) catalyst switched the regioselectivity to give (Z)-alpha-alkynylmethyl(alkenyl)stannanes. The acylstannylation products were successfully converted into various conjugated or unconjugated enones by a combination of cross-coupling and NaH-catalyzed isomerization. The alkynylstannylation products were transformed by cross-or homo-coupling reactions to various enynes or 2,3-bis(alkynylmethyl)-1,3-dienes, versatile precursors for variously substituted polycyclic compounds.

• 出版日期2004-11-15