Organic Synthesis Utilizing the Transformation of Thioacetals into Titaniumcarbene Complexes
Organic Synthesis Utilizing the Transformation of Thioacetals into Titaniumcarbene Complexes
复制标题
利用硫缩醛转化为钛碳烯配合物的有机合成
DOI：
10.5059/yukigoseikyokaishi.56.1048
复制
发表时间：
1998
影响因子：
0.2
通讯作者：
T. Fujiwara
中科院分区：
文献类型：
--
作者：
T. Takeda*;T. Fujiwara
最近，我们发现，各种钛-卡宾配合物产生的硫代缩醛与低价钛物种Cp 2 Ti [P（OEO）3] 2的脱硫。本文介绍了它们在有机合成中的应用，并提出了一些指导性的概念。由α，β-不饱和醛或1，3-二苯硫基丙烯衍生物制备的硫代缩醛在1-烯烃存在下脱硫得到烯基环丙烷。该反应的中间体乙烯基卡宾配合物与羰基化合物反应，以良好的产率得到Wittig样烯化产物。使用各种类型的硫代缩醛和原硫代甲酸酯与包括羧酸衍生物的羰基化合物的类似羰基烯化也产生各种烯烃。此外，由饱和硫代缩醛形成的亚烷基二茂钛与具有碳-碳多重键的有机分子反应。当它们与炔反应时，以高的立体选择性生成共轭二烯。与烯丙基三烷基硅烷反应生成（Z）-γ-取代烯丙基硅烷，生成钛环丁烷中间体。我们还发现了钛-卡宾配合物与三烷基硅烷和相关的14族有机金属化合物的第一个[2+1]类卡宾插入反应。
Recently we found that various titanium-carbene complexes were produced by the desulfurization of thioacetals with the low-valent titanium species Cp2Ti [P (OEO)3] 2. This article deals with their application to organic synthesis including some guiding conceptions of the study. Desulfurization of thioacetals prepared from α, β-unsaturated aldehydes or 1, 3-bis (phenylthio) propene derivatives in the presence of 1-olefins afforded alkenylcyclopropanes. The intermediates of this reaction, vinylcarbene complexes, reacted with carbonyl compounds to afford the Wittig-like olefination products in good yields. The similar carbonyl olefination using various types of thioacetals and orththioformates with carbonyl compounds including carboxylic acid derivatives also produced a variety of olefins. Furthermore the alkylidenetitanocenes formed from saturated thioacetals reacted with organic molecules having a carbon-carbon multiple bond. When they were treated with alkynes, conjugated dienes were produced with high stereoselectivity. The reaction with allyltrialkylsilanes afforded (Z) -γ-substituted allylsilanes via the formation of titanacyclobutane intermediates. We also found the first [2+1] carbenoid insertion reaction of titanium-carbene complexes with trialkylsilanes and related group 14 organometallics.