Development of Synthetic Organic Reactions Based on Novel Characteristic Behavior of Highly Coordinated Transition Metal Complexes

基于高度配位过渡金属配合物新特征行为的合成有机反应的发展

• 批准号: 11650882
• 负责人: HOJO Makoto
• 金额: $ 2.3万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650882/
• 关键词: manganese; chromium; ate complex; iron; catalyst; thiomethyl; allyl; carbolithiation; カルボメタル化; 有機亜鉛; アルキルリチウム; 3置換アルケン; 分子内環化

In contrast to ate-complexes based on main-group elements, transition-metal ate complexes are expected to be reductants besides alkylating agents, since the ate-complexes, the electron-excess system may react with electrophiles through the oxidative addition. We planed to investigate the reductive behavior of the transition metal ate complexes and found the direct and reductive generation of organometallic reagents starting from several electrophiles.Thus tributylmanganate reagent reacted with iodomethyl sulfides to produce the corresponding thiomethylmanganese reagents. In this reaction, metal-halogen exchange reaction proceeds rapidly even at-78℃, while the oxidative addition of iodomethyl sulfide to the manganese ate complex takes place predominantly at -20℃. Thiomethylmanganese reagents react with allyl bromides, enones, and aldehydes.Chromium ate complexes also reduce allyl phosphates to generate allylchromium reagents. We also found iron-catalyzed carbolithiation of alkynes, where the regio-and stereochemically defined multi-substituted vinyllithium reagents were produced. In this reaction, ate-type complex based on low valent iron is thought to be an actual catalyst.

与基于主族元素的配合物相比，过渡金属配合物除了作为烷基化剂之外，还可以作为还原剂，因为配合物中的过量电子体系可以通过氧化加成与亲电试剂反应。我们计划研究过渡金属配合物的还原行为，发现从几种亲电试剂出发，可以直接还原生成有机金属试剂，即三丁基溴化铵试剂与碘甲基硫醚反应生成相应的硫甲基锰试剂。在该反应中，金属-卤素交换反应在-78 ℃下迅速进行，而碘甲硫醚与锰配合物的氧化加成反应主要在-20℃下进行。硫代甲基锰试剂与烯丙基溴、烯酮和醛反应。铬酸盐络合物也可还原烯丙基磷酸酯生成烯丙基铬试剂。我们还发现了铁催化的炔的碳锂化反应，其中产生了区域和立体化学定义的多取代乙烯基锂试剂。在该反应中，基于低价铁的酸盐型络合物被认为是实际的催化剂。

项目成果

M.Hojo: "Iron-Catalyzed Regio- and Stereoselective Carbolithiation of Alkynes"Angew.Chem.Int.Ed.. 40・3. 621-623 (2001)

M.Hojo：“炔烃的铁催化区域选择性碳锂化”Angew.Chem.Int.Ed. 40・3（2001）。

M.Hojo: "Iron-Catalyzed Regio-and Stereoselective Carbolithiation of Alkynes"Angew.Chem., Int.Ed.. 40・3. 621-623 (2001)

M.Hojo：“炔烃的铁催化区域选择性碳锂化”Angew.Chem.，Int.Ed. 40・3（2001）。

Makoto Hojo: "Allyl-and propargylchromium reagents generated by a chromium (III) ate-type reagent as a reductant and their reactions with electrophiles"Chem.Commun.. (4). 357-358 (2001)

Makoto Hojo：“由铬 (III) 型试剂作为还原剂生成的烯丙基和炔丙基铬试剂及其与亲电子试剂的反应”Chem.Commun. (4)。

M.Hojo: "Allyl-and propargylchromium reagents generated by a chromium (III) ate-type reagent as a reductant and their reactions with electrophiles"Chem.Commun.. ・4. 357-358 (2001)

M.Hojo：“由铬(III)型试剂作为还原剂生成的烯丙基和炔丙基铬试剂及其与亲电子试剂的反应”Chem.Commun. ・4。

M.Hojo: "New Reactivity of Methoxyhydridosilane in the Catalytic Activation System"Tetrahedron Lett.. 37・51. 9241-9244 (1999)

M.Hojo：“催化活化体系中甲氧基氢硅烷的新反应性”Tetrahedron Lett.. 37・51（1999）