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。

公开(公告)号：US06590048B1

公开(公告)日：2003-07-08

申请号：US09555652

申请日：2001-01-02

申请人： Alois Fürstner ,  Pierre Dixneuf ,  Christian Bruneau ,  Michel Picquet

发明人： Alois Fürstner ,  Pierre Dixneuf ,  Christian Bruneau ,  Michel Picquet

IPC分类号： C07C604

CPC分类号： B01J31/2265 ,  B01J31/2295 ,  B01J31/24 ,  B01J31/2404 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C07C6/04 ,  C07C2531/22 ,  C07C2531/24 ,  C07F15/002 ,  C07F15/0046

摘要： The present invention describes the use of cationic vinylidene, allenylidene and higher cumulenylidene complexes of ruthenium or osmium as catalysts or catalyst precursors for olefin metathesis reactions of all types, as well as to new cationic allenylidene complexes of ruthenium and osmium which can be used as metathesis catalysts with preferred embodiment. These catalysts or catalyst precursors are easy to prepare from well accessible, stable and essentially non toxic starting materials, can be isolated and stored, they exhibit a high catalytic activity, a good compatibility with functional groups, solvents, water and additives, and they need not to be activated by any additive. Olefins of all types can be used as the substrates in the present invention in ring closing metathesis (RCM) of acyclic dienes and polyenes, the metathesis of enynes and dienynes, the ring opening metathesis polymerization (ROMP) of cyclic olefins, the acyclic diene metathesis polymerization (ADMET) of acyclic dienes or polyenes, the depolymerization of olefinic polymers, and the cross metathesis of two or more olefins. The present invention also applies to combinations of these types of metathetic reactions and domino processes thereof.

摘要翻译： 本发明描述了使用钌或锇的阳离子亚乙烯基，亚烯基亚乙基和更高的亚ul烯基络合物作为所有类型的烯烃复分解反应的催化剂或催化剂前体，以及可用作复分解的钌和锇的新的阳离子亚烯基亚化复合物。 催化剂。 这些催化剂或催化剂前体易于从易于获得的，稳定的和基本上无毒的原料制备，可以分离和储存，它们具有高催化活性，与官能团，溶剂，水和添加剂的良好相容性，并且它们需要 不被任何添加剂活化。 所有类型的烯烃可以用作本发明的无环二烯和多烯的闭环复分解（RCM）中的底物，烯烃和二烯的复分解，环烯烃的开环易位聚合（ROMP），无环二烯复分解 无环二烯或多烯的聚合（ADMET），烯烃聚合物的解聚和两种或多种烯烃的交叉复分解。 本发明也适用于这些类型的复分解反应和多米诺骨牌过程的组合。

公开(公告)号：US06348551B1

公开(公告)日：2002-02-19

申请号：US09403331

申请日：1999-10-15

申请人： Alois Fürstner ,  Walter Leitner ,  Daniel Koch ,  Klaus Langemann ,  Christian Six

发明人： Alois Fürstner ,  Walter Leitner ,  Daniel Koch ,  Klaus Langemann ,  Christian Six

IPC分类号： C08F472

CPC分类号： C07D315/00 ,  C07B37/10 ,  C07C29/00 ,  C07C45/673 ,  C07C49/607 ,  C07C2601/10 ,  C07D207/20 ,  C07D207/48 ,  C07D267/00 ,  C07D307/28 ,  C07D313/00 ,  C07D321/00 ,  C07C35/50

摘要： Cyclic products are prepared by selective olefin metathesis of bifunctional or polyfunctional substrates in the presence of one or several homogeneous or heterogeneous metathesis catalysts in a reaction medium. The invention is characterized in that the substrates contain two or more functional groups in the form of substituted or non-substituted alkene or alkyne units and in that the reaction medium essentially consists of compressed carbon dioxide. Also disclosed is the preparation of cyclic or polymer products according to the disclosed process, the reaction temperature and total pressure being matched to ensure that the density of the reaction medium lies in a range d=0.2-1.5 g·cm−3 and that the product distribution is essentially controlled by the reaction medium density.

摘要翻译： 在反应介质中存在一种或几种均相或非均质的复分解催化剂的情况下，通过双功能或多官能底物的选择性烯烃复分解制备环状产物。 本发明的特征在于，底物含有两个或多个取代或未取代的烯烃或炔单元形式的官能团，并且反应介质基本上由压缩二氧化碳组成。 还公开了根据所公开的方法制备环状或聚合物产物，反应温度和总压力相匹配，以确保反应介质的密度在d = 0.2-1.5g·cm -3的范围内， 产物分布基本上由反应介质密度控制。

公开(公告)号：US08431724B2

公开(公告)日：2013-04-30

申请号：US12532524

申请日：2008-03-05

申请人： Alois Fürstner ,  Christina Nevado-Blàzquez ,  Mario Waser ,  Emilie Moulin ,  Christophe Aïssa

发明人： Alois Fürstner ,  Christina Nevado-Blàzquez ,  Mario Waser ,  Emilie Moulin ,  Christophe Aïssa

IPC分类号： C07D313/04

CPC分类号： C07D313/00

摘要： The invention relates to Iejimalides having the following formula (I) in which a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p are simple or double bonds, the continuous lines representing at least one simple bond, the dotted lines representing a possible bond. A double bond can be present but it is not necessary, and provided that a continuous line is also present, or a simple bond can be present if no other line is represented; m=0-20 and n1-n18=1, 2. The bonds can be used as chemotherapeutic agents for treating cancer.

摘要翻译： 本发明涉及具有下列通式（I）的吡嗪酮，其中a，b，c，d，e，f，g，h，i，j，k，l，m，n，o，p是简单或双键 ，连续线表示至少一个简单的键，虚线表示可能的键。 可以存在双键，但是不存在连续线，或者如果没有其它线被表示，则可以存在简单的键; m = 0-20，n1-n18 = 1,2。这些键可用作治疗癌症的化学治疗剂。

公开(公告)号：US20100056616A1

公开(公告)日：2010-03-04

申请号：US12532524

申请日：2008-03-05

申请人： Alois Fürstner ,  Christina Nevado-Blàzquez ,  Mario Waser ,  Emilie Moulin ,  Christophe Aïssa

发明人： Alois Fürstner ,  Christina Nevado-Blàzquez ,  Mario Waser ,  Emilie Moulin ,  Christophe Aïssa

IPC分类号： A61K31/335 ,  C07D313/00 ,  A61P35/00

CPC分类号： C07D313/00

摘要： The invention relates to Iejimalides having the following formula (I) in which a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p are simple or double bonds, the continuous lines representing at least one simple bond, the dotted lines representing a possible bond. A double bond can be present but it is not necessary, and provided that a continuous line is also present, or a simple bond can be present if no other line is represented; m=0-20 and n1-n18=1, 2. The bonds can be used as chemotherapeutic agents for treating cancer.

摘要翻译： 本发明涉及具有下列通式（I）的吡嗪酮，其中a，b，c，d，e，f，g，h，i，j，k，l，m，n，o，p是简单或双键 ，连续线表示至少一个简单的键，虚线表示可能的键。 可以存在双键，但是不存在连续线，或者如果没有其它线被表示，则可以存在简单的键; m = 0-20，n1-n18 = 1,2。这些键可用作治疗癌症的化学治疗剂。

公开(公告)号：US07026478B2

公开(公告)日：2006-04-11

申请号：US10143404

申请日：2002-05-10

申请人： Alois Fürstner ,  Andreas Leitner ,  María Méndez

发明人： Alois Fürstner ,  Andreas Leitner ,  María Méndez

IPC分类号： C07D237/00 ,  C07D237/02 ,  C07D487/00 ,  C07D251/00 ,  C07D239/02 ,  C07D215/00 ,  C07D215/04 ,  C07D215/12 ,  C07C69/76 ,  C07C303/00

CPC分类号： C07D213/64 ,  C07C1/326 ,  C07D213/06 ,  C07D213/16 ,  C07D215/06 ,  C07D217/02 ,  C07D237/08 ,  C07D239/38 ,  C07D239/74 ,  C07D241/12 ,  C07D241/42 ,  C07D251/20 ,  C07D487/04

摘要： A process for the production of compounds Ar—R1 by means of a cross-coupling reaction of an organometallic reagent R1-M with an aromatic or heteroaromatic substrate Ar—X catalyzed by one or several iron salts or iron complexes as catalysts or pre-catalysts, present homogeneously or heterogeneously in the reaction mixture. This new invention exhibits substantial advantages over established cross coupling methodology using palladium- or nickel complexes as the catalysts. Most notable aspects are the fact that (i) expensive and/or toxic nobel metal catalysts are replaced by cheap, stable, commercially available and toxicologically benign iron salts or iron complexes as the catalysts or pre-catalysts, (ii) commercially attractive aryl chlorides as well as various aryl sulfonates can be used as starting materials, (iii) the reaction can be performed under “ligand-free” conditons, and (iv) the reaction times are usually very short.

摘要翻译： 通过有机金属试剂R 1 -M与芳族或杂芳族底物Ar-X的交叉偶联反应生产化合物Ar-R 1的方法 由一种或多种铁盐或铁络合物催化，作为催化剂或预催化剂，在反应混合物中均匀或不均匀地存在。 与使用钯或镍络合物作为催化剂的已建立的交联方法相比，该新发明显示出显着的优点。 最显着的方面是（i）昂贵的和/或有毒的诺贝尔金属催化剂被廉价的，稳定的，可商购的和毒理学上良好的铁盐或铁络合物替代为催化剂或预催化剂，（ii）商业上吸引人的芳基氯化物 以及各种芳基磺酸盐可以用作原料，（iii）反应可以在“无配体”条件下进行，（iv）反应时间通常很短。