Nickel-catalyzed cross-couplings involving carbon-oxygen bonds.
Nickel-catalyzed cross-couplings involving carbon-oxygen bonds.
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DOI：
10.1021/cr100259t
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发表时间：
2011-03-09
期刊：
影响因子：
62.1
通讯作者：
Percec, Virgil
中科院分区：
文献类型：
--
作者：
Rosen, Brad M.;Quasdorf, Kyle W.;Wilson, Daniella A.;Zhang, Na;Resmerita, Ana-Maria;Garg, Neil K.;Percec, Virgil
回顾复杂的分子拓扑结构和结构。为了将分子梦想变成现实，合成化学家必须最终卷起袖子，成为分子建筑工人，一砖一瓦地建造他们的结构。从波义耳、道尔顿和拉瓦锡时代的现代化学的黎明到今天，分子构建的工具已经发展，经历了从原子论理论的发展到专注于药用天然产物的对映选择性合成的逆合成方法的严格应用的显著范式转变。1-3最近，学术界和工业界的焦点已经转向高效化学，利用低成本和绿色试剂，从生物来源的原料开始设计高原子经济性的转化，以及在生产设计的大分子材料4和超分子系综的策略中超越小分子。已经探索了许多策略来合成相对较大的有机分子和聚合物，但通常将预制单元偶联在一起更迅速。7-15在同偶联（homocoupling）、相同化学片段的连接和交叉偶联的早期发展中，早期的过渡金属如Ni被认为是有用的试剂和催化剂。然而，在中间的几年里，更多的注意力被投入到后期过渡金属催化的开发上，特别是Pd催化的Heck，16，17 Hiyama，18 Kumada，19 Negishi，20，21 Suzuki-Miyaura，22，23 Sonogashira，24和Stille 25，26偶联技术，由于在可降解催化剂的多样性和可持续性方面的一些优势，它们的氧化和水稳定性，以及它们的络合物的相对容易的分离和结构分析，这有助于机理和方法学的发展。这些通常为Pd催化的偶联反应使用多种有机金属金属转移试剂或不饱和官能团用于配位/插入化学，但几乎一致地需要芳基、乙烯基、烯丙基或有时烷基卤化物作为亲电子试剂。虽然这份手稿正在修订中，但Pd催化的交叉偶联的开创性工作获得了2010年诺贝尔化学奖，由Heck教授，Negishi教授和Suzuki教授获得。然而，人们越来越关注使用更容易获得的、经济的和环境友好的苯酚和烯醇衍生的亲电试剂。苯酚和烯醇衍生的亲电试剂的价值工业化学家现在能够为实验室化学家提供各种各样的芳基、多芳基、乙烯基、烯丙基和烷基卤化物。然而，这些物种从天然来源中获得的机会要少得多，并且肯定不会在生物合成途径中用作偶联伴侣。酚和烯醇衍生的亲电试剂的一个关键优点是这些底物的容易接近性。在酚的情况下，这样的化合物是天然丰富的或可以容易地从其他容易获得的芳族物质制备。28 Scifinder的一项研究表明，有超过50 000种苯酚和芳基多元醇衍生物可在市场上买到。此外，对于某些杂芳族化合物，酚型取代基通常可以衍生自内酰胺前体。烯醇衍生的亲电试剂的优点是类似的，因为这类交叉偶联伴侣可以通过烯醇化和随后捕获容易获得的羰基化合物来获得。使用酚衍生的亲电试剂存在其它优点。最值得注意的是，芳环上的氧化可以通过许多途径引入额外的取代基，包括亲电芳族取代...
REVIEW intricate molecular topologies and architectures. To turn the molecular dreams into a reality, synthetic chemists must ultimately roll up their sleeves and become molecular construction workers building their structure brick by brick. From the dawn of the modern chemistry in the ages of Boyle, Dalton, and Lavoisier to the present days, the tools for molecular construction have evolved, progressing through notable paradigm shifts from the development of the atomistic theory to the rigorous application of the retrosynthetic method focusing on the enantioselective synthesis of medicinal natural products. 1-3 More recently, academic and industrial focus has moved toward efficient chemistry utilizing low-cost and green reagents in transformations designed with high atom-economy starting from biosourced feedstocks as well as beyond the small molecule in strategies to produce designed macromolecular materials4 and supramolecular ensembles. 5, 6 Numerous strategies have been explored for the synthesis of relatively large organic molecules and polymers, but typically the coupling of prefabricated units together is more expeditious. 7-15 Early in the development of homocoupling, the joining of identical chemical fragments, and cross-coupling, early transition metals such as Ni were identified as useful reagents and catalysts. However, in the intervening years more attention was invested in the development of later transition metal catalysis, particularly Pd-catalyzed Heck, 16, 17 Hiyama, 18 Kumada, 19 Negishi, 20, 21 Suzuki-Miyaura, 22, 23 Sonogashira, 24 and Stille25, 26 coupling techniques, due to some advantages in terms of the diversity and tenability of preparable catalysts, their oxidative and aqueous stability, and relatively facile isolation and structural analysis of their complexes, which aided mechanistic and methodologic developments. These, typically Pd-catalyzed, 27 coupling reactions used a diversity of organometallic transmetalating reagents or unsaturated functionalities for coordination/insertion chemistry, but nearly uniformly required aryl, vinyl, allyl, or sometimes alkyl halides as electrophiles. While this manuscript was under revision, the pioneering work on Pd-catalyzed cross-coupling was recognized with the 2010 Nobel Prize in Chemistry for Professors Heck, Negishi, and Suzuki. However, there is growing interest in using more available, economical, and environmentally friendly phenol-and enol-derived electrophiles.1.2. Value of Phenol-and Enol-Derived Electrophiles Industrial chemists are now able to provide a wide array of aryl, polyaryl, vinyl, allyl, and alkyl halides to the hands of bench chemists. However, such species are far less available from natural sources and are certainly not used as coupling partners in biosynthetic pathways. A key benefit to phenol-and enol-derived electrophiles is the ready accessibility of these substrates. In the case of phenols, such compounds are naturally abundant or can be readily prepared from other easily accessed aromatic species. 28 A Scifinder search reveals that over 50 000 phenol and aryl polyol derivatives are commercially available. 29 Moreover, for certain heteroaromatic compounds, a phenol-type substituent can often be derived from a lactam precursor. The advantages are similar for enol-derived electrophiles, as cross-coupling partners of this class can be accessed by enolization and subsequent trapping of readily available carbonyl compounds. Other advantages to using phenol-derived electrophiles exist. Most notably, oxygenation on the aromatic ring can be used to introduce additional substituents via a number of pathways including electrophilic aromatic substitution …
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影响因子：
1.7
作者：
Alonso, F;Radivoy, G;Yus, M
通讯作者：
Yus, M
影响因子：
2.8
作者：
Berding, Joris;Lutz, Martin;Bouwman, Elisabeth
通讯作者：
Bouwman, Elisabeth
影响因子：
15
作者：
Alvarez-Bercedo, Paula;Martin, Ruben
通讯作者：
Martin, Ruben
影响因子：
4
作者：
Berding, Joris;van Dijkman, Thomas F.;Bouwman, Elisabeth
通讯作者：
Bouwman, Elisabeth
影响因子：
15
作者：
Antoft-Finch, Aurora;Blackburn, Tom;Snieckus, Victor
通讯作者：
Snieckus, Victor