Reversible carbon-carbon bond formation between 1,3-dienes and aldehyde or ketone on nickel(0)
Reversible carbon-carbon bond formation between 1,3-dienes and aldehyde or ketone on nickel(0)
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DOI：
10.1021/ja060580l
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发表时间：
2006-05-31
影响因子：
15
通讯作者：
Kurosawa, Hideo
中科院分区：
文献类型：
--
作者：
Ogoshi, Sensuke;Tonomori, Kei-ichi;Kurosawa, Hideo
二烯和醛与镍(0)进行可逆氧化环化反应，得到eta(3):eta(1)-烯丙基烷氧镍配合物。这些配合物与一氧化碳的处理导致形成相应的内酯和/或再生丁二烯和醛，同时形成Ni(CO)(3)（PCy3）。烯丙烷氧配合物与ZnMe2断裂镍氧键生成eta(3)-烯丙基（甲基）镍，可以有效抑制氧化环化的逆反应。甲基化的eta(3)-烯丙基镍化合物进行了还原消除。在一氧化碳气氛下，eta(3)-烯丙基（甲基）镍的羰基偶联反应也进行了。同样，将Me3SiCl加入eta(3):eta(1)-烯丙基烷氧镍配合物中也能有效抑制逆反应。得到的eta(3)-1-硅氧乙基烯基镍配合物用一氧化碳处理，然后加入甲醇得到预期的羟基聚酯。这种方法对于含有丙酮的eta(3):eta(1)-烯丙基（烷氧基）镍配合物也是有效的，因为该配合物容易发生逆反应，阻碍了其分离。采用较重的丁二烯和酮，如2,3-二苯并-1,3-丁二烯和二苯甲酮，或采用环丁酮，可使以酮为组分的eta(3):eta(1)-烯丙基烷氧镍配合物的分离更容易。与氧化苯乙烯反应得到eta(3):eta(1)-烯丙基烷氧镍，含有苯乙烯的异构体苯乙醛。
The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give eta(3):eta(1)-allylalkoxynickel complexes. The treatment 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)(PCy3). The scission of the nickel-oxygen bond of the allylalkoxy complexes with ZnMe2 leading to eta(3)-allyl(methyl) nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated eta(3)-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the eta(3)-allyl(methyl) nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me3SiCl to eta(3):eta(1)-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting eta(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 eta(3):eta(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 the eta(3):eta(1)-allylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadiene and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the eta(3):eta(1)-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide.