Development of New and Efficient Organic Transformations Catalyzed by Molybdenum

钼催化的新型高效有机转化的发展

• 批准号: 17590021
• 负责人: SUGIHARA Takumichi
• 金额: $ 2.24万
• 依托单位: Nigata University of Phermacy and Applied Life Sciences
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17590021/
• 关键词: molybdenum; catalyst; n-ligand; propargyl bromide; allyl substitution; cvclization; カルボニル錯体; 臭化アリル; アレン; 置換反応; π-アリル錯体; ブロモジエン; アルキン; ベンゼン; シクロヘキサジエン

We developed a new catalyst based on molybdenum, which was made in situ by reaction of molybdenum hexacarbonyl with Propargyl bromide. The catalyst promoted [2+2+2]-cocyclization of diynes having both terminal alkynes with propargyl bromide to produce substituted benzyl bromide derivatives. When diynes had both terminal and internal alkynes, the reaction with propargyl bromide produced cyclized bromodiene derivative without incorporation of alkyne part of propargyl bromide. In addition, reaction of allenylmethyl acetate with propargyl bromide catalyzed by n-propargylmolubdenum gave 2-bromo-1,3-butadiene derivatives. The scope and limitation of these reactions was also investigated. Since no other transition metal complexes mediated these reactions, our findings should be inherent organic transformations of molybdenum.

以六羰基钼与丙炔溴原位反应制备了一种新型钼基催化剂。催化剂促进具有两个末端炔的双炔与丙炔溴的[2+2+2]-共环反应生成取代苯溴衍生物。当双炔同时含有端炔和内炔时，与丙炔溴的反应生成环化溴二烯衍生物，而不含丙炔溴的炔部分。此外，在正丙基钼的催化下，醋酸丙烯甲基与丙炔溴反应得到了2-溴-1,3-丁二烯衍生物。研究了这些反应的范围和局限性。由于没有其他过渡金属配合物介导这些反应，我们的发现应该是钼固有的有机转化。