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首页> 外文期刊>Chemistry: A European journal >Up to Seven-Component Adducts by Unprecedented Multiple Alkyne and Carbonyl Insertions in the Metal-Carbon Bond of Chromium Alkoxy Alkynyl Carbene Complexes
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Up to Seven-Component Adducts by Unprecedented Multiple Alkyne and Carbonyl Insertions in the Metal-Carbon Bond of Chromium Alkoxy Alkynyl Carbene Complexes

机译：前所未有的多个炔烃和羰基在铬烷氧基炔基碳烯配合物的金属-碳键中的插入，最多可形成七组分加合物

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摘要

Chromium alkoxy alkynyl Fischer carbene complexes react with symmetrical internal alkynes to form new and different organometallic species,which result from consecutive insertions of several alkyne units and carbonyl groups into the metal-carbon bond.The insertion sequence can be controlled and,by slight modification of the reaction conditions,it can be directed to the preparation of either seven-or five-component adducts.Three molecules of alkyne,two carbonyl groups,the carbene ligand and the chromium metal moiety partake in the creation of seven new carbon-carbon bonds and two five-membered carbocy-cles in the first case while four new carbon-carbon bonds,a sigma Cr-C(sp~2)bond and a cyclopentadienyl moiety are built in the second case.Evidence that five-component chromium complexes are intermediates in the formation of seven-component adducts is provided;they are also able to insert a unit of a different internal alkyne which confers more diversity to the seven-component adducts.The presence of the sigma Cr-C(sp~2)bond has also been exploited to develop the synthesis of both cyclopentene-fused and novel spiro-cyclopentenones as well as symmetrical biscyclopentenones.Finally,the isolation of six-component adducts,when tolane was employed as the initial alkyne,provides further support to the proposed mechanism.
机译：铬烷氧基炔基菲舍尔卡宾络合物与对称内部炔烃反应形成新的和不同的有机金属物质，这是由于几个炔烃单元和羰基连续插入金属-碳键中引起的。插入顺序可以通过控制和稍加修饰来控制该反应条件可用于制备七或五组分加合物。炔烃的三个分子，两个羰基，卡宾配体和铬金属部分参与创建七个新的碳-碳键和第一种情况是两个五元碳环，而第二种情况是建立了四个新的碳-碳键，σCr-C（sp〜2）键和环戊二烯基部分。证据表明五组分铬络合物是中间体提供了七组分加合物的形成方法;它们还能够插入不同内部炔烃的单元，从而使七组分加合物具有更多多样性。还利用了sigma Cr-C（sp〜2）键的存在来开发环戊烯稠合的和新颖的螺环戊烯酮以及对称的双环戊烯酮的合成方法。最后，分离六组分加合物时作为初始炔烃使用，为拟议的机制提供了进一步的支持。

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