Generation and Reaction of Multi-functionalized Transition Metal Reactive Species

本研究对新型多功能活性物种的产生和反应进行了深入的研究。通过W（CO）_5（L）亲电活化炔类化合物，再用亲核试剂进攻炔类化合物，可以得到具有1，3-偶极和卡宾配合物双重性质的多功能活性物种。基于这一概念，人们发展了几种独特的合成有用的反应：首先，发展了新型含钨羰基叶立德和甲亚胺叶立德的生成和反应。W（CO）_5（thf）处理邻乙炔基苯基酮或N-（邻炔基苯基）亚胺衍生物，通过羰基氧或亚氨基氮对亲电活化的炔部分的内进攻方式生成含钨的1，3-偶极。生成的叶立德与富电子烯烃的[3+2]-环加成，然后将所得钨卡宾部分插入相邻的C-H键或1，2- ...更多信息 烷基迁移实现了在单一步骤中构建复杂的环状碳骨架。该反应在催化量W（CO）_5（thf）存在下也能进行。因此，新的多功能活性物种被成功地产生，并在一个单一的操作中与烯烃反应，得到合成有用的化合物。ω-炔二烯醇硅醚与W（CO）_6在光辐射下反应，得到双环[3.3.0]辛烷衍生物，再与亲电活化的炔加成，得到烯基金属中间体。它进一步与金属β位的α，β-不饱和氧鎓基团反应，得到卡宾配合物中间体，再经过典型的卡宾反应得到产物。该方法构成了用于炔的偕碳官能化的催化方法。ReCl（CO）_5对该反应有很高的催化活性，当ReCl（CO）_5的摩尔分数为0.5 ~ 3.0%时，反应仍能进行。少

In this research, generation and reaction of novel multi-functional reactive species are studied extensively. It is expected that electiophilic activation of alkynes with W(CO)_5(L) followed by attack of nucleophiles on them would give novel multi-functional reactive species, which are expected to behave both as a 1,3-dipole and as a carbene complex. Based on this concept, several unique and synthetically useful reactions have been developed.In the first place, generation and reaction of novel tungsten-containing carbonyl and azomethine ylides were developed. Treatment of ο-ethynylphenyl ketones or N-(ο-alkynylphenyl)imine derivatives with W(CO)_5(thf) generated the tungsten-containing 1,3-dipoles by the endo-mode of attack of the carbonyl oxygen or imino nitrogen onto the electrophilically activated alkyne moiety. The [3+2]-cycloaddition of the generated ylides with electron-rich alkenes followed by insertion of the resulting tungsten carbene moiety into a neighboring C-H bond or 1,2- … More alkyl-migration realized the construction of complex cyclic carbon frameworks in a single step. This reaction proceeded even with a catalytic amount of W(CO)_5(thf). Thus, novel multi-functional reactive species are successfully generated and react with alkenes to give synthetically useful compounds in a single operation.We next examined the possibility of realizing geminal carbo-functionalization of alkynes. Treatment of ω-acetylenic dienol silyl ethers with W(CO)_6 under photoirradiation gave bicyclo[3.3.0]octane derivatives, which were produced by addition of the silyl enol ether to the electrophilically activated alkynes to give alkenylmetallic intermediates. This further reacted with α,β-unsaturated oxonium moiety at the position β to the metal to give carbene complex intermediates, which underwent typical carbene reactions to give the products. This method constitutes a catalytic method for the geminal carbo-functionalization of alkynes. ReCl(CO)_5 showed paiticularly high activity for this reaction ; even 0.5〜3.0 mol% of ReCl(CO)_5 were sufficient to promote the reaction efficiently. Less