公开(公告)号：US06525197B1

公开(公告)日：2003-02-25

申请号：US09601632

申请日：2000-08-04

申请人： Alois Fürstner ,  Günter Seidel ,  Antonio Rumbo ,  Christian Mathes

发明人： Alois Fürstner ,  Günter Seidel ,  Antonio Rumbo ,  Christian Mathes

IPC分类号： A61K3133

CPC分类号： C07D315/00 ,  C07B37/10 ,  C07D245/02 ,  C07D321/00 ,  C07D491/04

摘要： The present invention relates to methods for preparing macrocyclic products having 9 or more ring atoms by ring-closing diyne metathesis of suitable diyne substrates. The diyne substrates can be converted into cycloalkynes or into cycloalkadiynes by cyclodimerization, depending on the particular reaction conditions. Any alkyne metathesis catalyst can be used as the catalyst, regardless of whether said catalysts are heterogeneously or homogeneously present in the reaction medium. The preferred catalysts or pre-catalysts are transition metal alkylidyne complexes, transition metal compounds which form alkylidyne complexes under the reaction conditions, and transition metal compounds with metal-metal triple bonds. The method can be carried out with numerous functional groups, solvents, and additives. Using known methods, the formed macrocyclic cycloalkynes or cycloalkadiynes can be converted into numerous secondary products, especially macrocyclic cycloalkenes with a uniform configuration of the double bond, and used, e.g., for the synthesis of epothilone or epothilone analogues.

摘要翻译： 本发明涉及通过合适的二炔底物的闭合二炔复分解制备具有9个或更多个环原子的大环产物的方法。 取决于具体的反应条件，二炔底物可以通过环二聚化转化为环炔或环炔二炔。 任何炔烃复分解催化剂都可以用作催化剂，而不管所述催化剂是不均匀还是均匀地存在于反应介质中。 优选的催化剂或预催化剂是过渡金属烷基炔配合物，在反应条件下形成亚烷基二炔配合物的过渡金属化合物和具有金属 - 金属三键的过渡金属化合物。 该方法可以用许多官能团，溶剂和添加剂进行。 使用已知的方法，形成的大环环炔或环链炔二炔可以转化为许多次级产物，特别是具有双键均匀构型的大环环烯烃，并且用于例如合成埃坡霉素或埃坡霉素类似物。