Regioselective Reductive Cross-Coupling Reactions of Unsymmetrical Alkynes.
Regioselective Reductive Cross-Coupling Reactions of Unsymmetrical Alkynes.
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DOI：
10.1002/ejoc.200901094
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发表时间：
2010-01
影响因子：
2.8
通讯作者：
Micalizio, Glenn C.
中科院分区：
文献类型：
--
作者：
Reichard, Holly A.;McLaughlin, Martin;Chen, Ming Z.;Micalizio, Glenn C.
本微观综述总结了我们的进展，在过去几年中，在定义区域选择性还原交叉偶联反应的不对称炔与终端和内部的炔，醛，亚胺。我们开始与一个简短的历史观点金属介导的还原二聚反应的芳香族炔，并讨论了与“交叉”版本的这种模式的反应性的挑战。接下来，收集可用的方法，允许区域选择性还原性交叉耦合的内部炔与终端和内部炔，醛，亚胺进行了总结。在这些情况下，区域选择性的要求检查后，我们的设计背后的逻辑醇盐导向的钛介导的还原性交叉偶联反应。一个命名法被引入到描绘与每个反应设计相关的区域选择性的假定的机理起源，和介绍的烷氧基定向的区域选择性还原交叉偶联反应的炔如下。在整个过程中，与反应性和选择性有关的主要问题进行了讨论，以评估可用方法的范围和局限性，并描述了广泛的挑战，存在定义复杂的片段工会反应的基础上还原交叉偶联化学。
The present microreview summarizes our progress over the last few years in defining regioselective reductive cross-coupling reactions of unsymmetrical alkynes with terminal- and internal alkynes, aldehydes, and imines. We begin with a brief historical perspective of metal-mediated reductive dimerization reactions of aromatic alkynes and discuss the challenges associated with “crossed” versions of this mode of reactivity. Next, a collection of available methods that allow for regioselective reductive cross-coupling of internal alkynes with terminal and internal alkynes, aldehydes, and imines is summarized. After an examination of the requirements for regioselectivity in these cases, the logic behind our design of alkoxide-directed titanium-mediated reductive cross-coupling reactions is presented. A nomenclature is introduced to delineate the presumed mechanistic origin of regioselection associated with each reaction design, and a presentation of alkoxide-directed regioselective reductive cross-coupling reactions of alkynes follows. Throughout, principal issues related to reactivity and selectivity are discussed to assess scope and limitations of available methods and to describe the broad challenges that exist for defining complex fragment union reactions based on reductive cross-coupling chemistry.
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影响因子：
15
作者：
Belardi, Justin K.;Micalizio, Glenn C.
通讯作者：
Micalizio, Glenn C.
影响因子：
62.1
作者：
Colby, Denise A.;Bergman, Robert G.;Ellman, Jonathan A.
通讯作者：
Ellman, Jonathan A.
影响因子：
15
作者：
Aoki, K;Peat, AJ;Buchwald, SL
通讯作者：
Buchwald, SL
影响因子：
3.6
作者：
BROWN, DC;NICHOLS, SA;THOMPSON, DW
通讯作者：
THOMPSON, DW
影响因子：
15
作者：
COHEN, SA;AUBURN, PR;BERCAW, JE
通讯作者：
BERCAW, JE