ORGANOTIN NUCLEOPHILES .5. PALLADIUM-CATALYZED ALLYLIC PROPARGYLATION WITH ALLENYLSTANNANE
ORGANOTIN NUCLEOPHILES .5. PALLADIUM-CATALYZED ALLYLIC PROPARGYLATION WITH ALLENYLSTANNANE
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DOI：
10.1021/jo00174a027
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发表时间：
1983-01-01
影响因子：
3.6
通讯作者：
PERETZ, M
中科院分区：
文献类型：
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作者：
KEINAN, E;PERETZ, M
在中性条件下，在催化量的Pd（PPh 3）4存在下，丙二烯基三烷基锡烷与各种乙酸烯丙酯发生反应，为获得1，5-烯炔碳骨架提供了一种新的途径.炔丙基化的区域选择性很大程度上取决于烯丙基体系两端取代基的吸电子性质：取代发生在更接近电负性基团的末端。烯丙基氰醇乙酸酯在氰基的a位被取代沿着形成还原的副产物。这些反应的几个机理方面进行了讨论。
Allenyltrialkylstannanes were found to react with various allylic acetates in the presence of catalytic amounts of Pd (PPh3) 4 under mild neutral conditions, providing a novel approach for obtaining the 1, 5-enyne carbon skeleton. The regioselectivity of propargylation depends largely on the electron-withdrawing properties of the substituents at the two ends of the allylic system: substitution occurs at the end of closer proximity to the more electronegative group. Allylic cyanohydrin acetates are substituted at a position a to the cyano group along with formation of a reduced side product. Several mechanistic aspects of these reactions are discussed.