Palladium-Catalyzed Coupling of Propargylic Carbonates with N-Tosylhydrazones: Highly Selective Synthesis of Substituted Propargylic N-Sulfonylhydrazones and Vinylallenes
Palladium-Catalyzed Coupling of Propargylic Carbonates with N-Tosylhydrazones: Highly Selective Synthesis of Substituted Propargylic N-Sulfonylhydrazones and Vinylallenes
复制标题
钯催化丙炔碳酸酯与 N-甲苯磺酰腙的偶联：高选择性合成取代的丙炔 N-磺酰腙和乙烯基联烯
DOI：
10.1002/chem.201100248
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发表时间：
2011-06-01
影响因子：
4.3
通讯作者：
Liang, Yong-Min
中科院分区：
文献类型：
--
作者：
Chen, Zi-Sheng;Duan, Xin-Hua;Liang, Yong-Min
钯催化炔丙基化合物与亲核试剂的反应是有机合成中最成功、最可靠的方法之一。[1]这些反应中的关键步骤是通过脱羧形成丙二烯基或π-炔丙基钯络合物（平衡过程），该络合物与其他亲核试剂进一步反应以提供不同种类的丙二烯、烯烃、炔和烯炔衍生物。[1]与此形成鲜明对比的是，钯催化的炔丙基碳酸酯与亲核试剂的炔丙基取代反应却很少受到关注。[2]这主要是因为大多数这些反应产生相应的联烯系统和随后的重排衍生物。[1]最近，开发了一种新型的Pd催化的重氮化合物的交叉偶联，并且已被证明是一种可靠的形成C13 C键的方法。[3]另一种途径是使用N-甲苯磺酰腙作为亲核试剂，因为它们很容易从相应的酮中获得。一些不稳定的重氮化合物也可以通过Bamford-Stevens-Shapiro反应由N-甲苯磺酰腙原位生成。[4]这种方法最初由Barluenga埃塔尔开发，已被证明可用于制备取代的烯烃。[5]然而，使用N-甲苯磺酰腙作为亲核试剂合成取代联烯的研究却少得多。据我们所知，只有一种最近的方法
The reaction of propargylic compounds with nucleophiles catalyzed by palladium is one of the most successful and reliable methods in organic synthesis.[1] The key step in these reactions is the formation of an allenyl-or π-propargylpalladium complex (an equilibrium process) by decarboxylation, which undergoes further reactions with other nucleophiles to afford different kinds of allene, alkene, alkyne, and enyne derivatives.[1] In sharp contrast, much less attention has been paid to the propargylic substitution reactions of propargylic carbonates with nucleophiles catalyzed by palladium.[2] This is mainly because most of these reactions give rise to the corresponding allenic systems and subsequent rearranged derivatives.[1]Recently, a new type of Pd-catalyzed cross-coupling of diazo compounds has been developed and it has been proven to be a reliable method for the formation of CÀC bonds.[3] An alternative route consists of using N-tosylhydrazones as nucleophiles because they are readily available from the corresponding ketones. Some unstable diazo compounds can also be generated in situ from N-tosylhydrazones through the Bamford-Stevens-Shapiro reaction.[4] This method, initially developed by Barluenga etal., has been proved to be useful for the preparation of substituted olefins.[5] However, the synthesis of substituted allenes using N-tosylhydrazones as nucleophiles is much less developed. To the best of our knowledge, there is only one recent method