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Bond Formation in Tight Coordination Sphere on Small Transition metal

小过渡金属上紧配位球中的键形成

基本信息

批准号：
16550096
负责人：
OGOSHI Sensuke
金额：
$ 2.62万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

The addition of 1,5-hexenal or o-allylbenzaldehyde to a solution of Ni(cod)_2 and PR_3 (PCy_3 or PPh_3,1 equiv) gave η^2-alkene:η^2-aldehyde complexes quantitatively. Heating the solution at 60℃ or 80℃ resulted in the oxidative cyclization to give nickelacycle complexes. The direct observation of oxidative cyclization from η^2-carbonyl:η^2-olefin coordination complex to five membered metalacycle has not been reported even with early transition metal systems. AlMe_3 promoted the oxidative cyclization of η^2:η^2-2-allylacetophenone- or η^2:η^2-2-allylbenzophenone nickel complex to give an intriguing nickel-aluminum dinuclear complex. The molecular structure was determined by X-ray diffraction analysis. This complex is a nice model as an intermediate in the transmetallation process. Moreover, the cycloisomerization can proceed catalytically in THF.The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give η^3:η^1-allylalkoxynickel complexes. The treatmen … More t of these complexes with carbon monoxide led to the formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant with the formation of Ni(CO)_3(PCy_3). The scission of nickel-oxygen bond of the allylalkoxy complexes with ZnMe_2 leading to η^3-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated η^3-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the η^3-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me_3SiCl to η^3:η^1-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting η^3-1-siloxyethylallylnickel complex was treated with carbon monoxides followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even for the η^3:η^1-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo the reverse reaction hampering its isolation. The isolation of η^3:η^1-qllylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadine and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the η^3:η^1-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide. Less

在Ni（cod）_2和PR_3（PCy_3或PPh_3，1当量）的溶液中加入1，5-己烯醛或邻烯丙基苯甲醛，定量地得到η^2-烯烃：η^2-醛络合物。在60℃或80℃下加热，可发生氧化环化反应，生成镍镧配合物。从η^2-羰基：η^2-烯烃配位化合物到五元金属配位化合物的氧化环化反应的直接观察甚至在早期过渡金属体系中也没有报道。AlMe_3促进了η^2：η^2-2-烯丙基苯乙酮-或η^2：η^2-2-烯丙基二苯甲酮镍配合物的氧化环化反应，得到了一种有趣的镍铝双核配合物。通过X射线衍射分析确定了分子结构。这个复合体是一个很好的模型，作为transmetabolism过程中的中间体。二烯和醛与镍（0）的可逆氧化环化反应得到了η^3：η^1-烯丙基烷氧基镍配合物。治疗 ...更多信息这些配合物与CO反应生成相应的内酯和/或再生一个丁二烯和一个醛，同时生成Ni（CO）_3（PCy_3）。烯丙基烷氧基配合物与ZnMe_2的镍-氧键断裂生成η^3-烯丙基（甲基）镍对抑制氧化环化反应的逆反应是非常有效的。甲基化的η^3-烯丙基镍化合物发生还原消除反应。η^3-烯丙基（甲基）镍的羰基化偶联反应也在一氧化碳气氛下进行。同样，在η^3：η^1-烯丙基烷氧基镍配合物中加入Me_3SiCl也能有效地抑制逆反应。用一氧化碳处理所得的η^3-1-羟乙基烯丙基镍络合物，然后加入MeOH，得到预期的羟基酯。该方法即使对于含有丙酮作为组分的η^3：η^1-烯丙基（烷氧基）镍络合物也是有效的，该络合物如此容易发生阻碍其分离的逆反应。用较重的丁二烯和酮（如2，3-二苄基-1，3-丁二烯和二苯甲酮）或环丁酮，可使含酮的η^3：η^1-烯基烷氧基镍配合物的分离变得容易。与氧化苯乙烯反应得到含苯乙醛的η^3：η^1-烯丙基烷氧基镍，它是氧化苯乙烯的异构体。少