N-tosylhydrazones as reagents for cross-coupling reactions:: A route to polysubstituted olefins
N-tosylhydrazones as reagents for cross-coupling reactions:: A route to polysubstituted olefins
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DOI：
10.1002/anie.200701815
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Aznar, Fernando
中科院分区：
文献类型：
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作者：
Barluenga, José;Moriel, Patricia;Aznar, Fernando
Pd催化的交叉偶联反应是目前合成C（sp2）→ C（sp2）键最可靠的方法。[1]这些类型的反应在复杂有机分子的合成中得到越来越多的应用。[2]在交叉偶联反应中，将亲电试剂与亲核试剂组合以提供相应的偶联产物（方案la）。有机试剂例如有机镁、[3]-锌、[4]-锡、[5]-硅、[6]和-硼[7]化合物等通常用作亲核组分。尽管这些方法具有广泛的适用性，但一般方法的局限性是需要化学计量量的有机金属试剂，在许多情况下，其必须通过昂贵的、湿敏的，和多步骤的程序。赫克反应（方案1b）可以被认为是C12 C键的最早的例子-形成不需要化学计量量的有机金属偶联配体的反应。[8]近年来，已经发现了一些不同于交叉偶联的其他实例：C1 H2键的直接活化[9]（方案1c），酮、[10]酯、[11]和酰胺的α-芳基化[12]（方案1d），以及
Pd-catalyzed cross-coupling reactions can be considered nowadays to be the most reliable methodology for the formation of C (sp2) ÀC (sp2) bonds.[1] These types of reactions find increasing application in the synthesis of complex organic molecules.[2] In a cross-coupling reaction, an electrophile is combined with a nucleophile to provide the corresponding coupling product (Scheme 1 a). Organometallic reagents such as organomagnesium,[3]-zinc,[4]-tin,[5]-silicon,[6] and-boron [7] compounds among others, are generally employed as the nucleophilic component. In spite of the wide applicability of these methodologies, a limitation of the general approach is the requirement of a stoichiometric amount of the organometallic reagent, which in many cases has to be prepared through expensive, moisture-sensitive, and multistep procedures.The Heck reaction (Scheme 1b) can be considered as the earliest example of a CÀC bond-forming reaction that does not require stoichiometric amounts of the organometallic coupling partner.[8] In recent years, some other examples have been discovered which differ from cross-coupling: the direct activation of CÀH bonds [9](Scheme 1c), the α-arylation of ketones,[10] esters,[11] and amides [12](Scheme1d), and the