Nickel-catalyzed acylstannylation and alkynylstannylation of 1,2-dienes |
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Authors: | Yoshiaki Nakao Teruhisa Tsuchimoto |
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Institution: | a Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan b Graduate School of Materials Science, Japan Advanced Institute of Science and Technology, Tatsunokuchi, Ishikawa 923-1292, Japan |
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Abstract: | 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 α-acylmethyl(vinyl)stannanes. The reaction was also applicable to acylstannanes prepared in situ by protonolysis of α-alkoxyalkenylstannanes or by reactions of α-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 α-alkynylmethyl(vinyl)stannanes, whereas the Ni(cod)2-1,3-bis(dimethylphosphino)propane (dmpp) catalyst switched the regioselectivity to give (Z)-α-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. |
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Keywords: | Nickel Carbometalation 1 2-diene Acylstanane Alkynylstannane |
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