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首页> 外文期刊>Journal of the American Chemical Society >Rh(ll)-Catalyzed Skeletal Reorganization of 1,6- and 1,7-Enynes through Electrophilic Activation of Alkynes
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Rh(ll)-Catalyzed Skeletal Reorganization of 1,6- and 1,7-Enynes through Electrophilic Activation of Alkynes

机译：Rh（ll）催化炔烃亲电活化1,6-和1,7-烯炔的骨架重组。

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摘要

The skeletal reorganization of 1,6- and 1,7-enynes leading to 1-vinylcycloalkenes using Rh(ll) as a catalyst is reported. Two possible isomers of 1 -vinylcycloalkenes, type I and type II, can be obtained, the ratio of which are highly dependent on the substitution pattern of the enynes used. Formation of type I compounds involves a single cleavage of a C-C double bond, the product of which is identical to that of enyne metathesis. In contrast, the formation of type II compounds involves the double cleavage of both the C-C double and triple bonds, which has an anomalous bond connection. The presence of both a phenyl group at the alkyne carbon and a methyl group at the internal alkene carbon facilitates the formation of type II compounds. The electronic and steric nature of the substituents on the aromatic ring also affects the ratio of type I and type II. The nature of a tether also has a significant effect on the course of the reaction. Experimental evidence for the intermediacy of a cyclopropyl rhodium carbenoid, a key intermediate in the skeletal reorganization of enynes, is also reported. In addition to the skeletal reorganization of enynes, Rh(ll) complexes were found to have a high catalytic activity for some cycloisomerization reactions of alkyne derivatives, including the bicyclization of enynes to bicyclo[4.1.0]heptene derivatives and the cyclization of alkynylfurans to phenol derivatives.
机译：据报道，使用Rh（II）作为催化剂的1，6-和1，7-烯炔的骨架重组产生1-乙烯基环烯烃。可以获得I-型和II-型的1-乙烯基环烯烃的两种可能的异构体，它们的比例高度依赖于所用烯炔的取代方式。 I型化合物的形成涉及C-C双键的单裂解，其产物与烯炔复分解的产物相同。相反，II型化合物的形成涉及具有异常键连接的C-C双键和三键的双裂解。炔碳上的苯基和内烯烃碳上的甲基的存在促进了II型化合物的形成。芳环上取代基的电子和空间性质也影响I型和II型的比例。系链的性质对反应过程也有重要影响。还报道了环丙基铑类胡萝卜素（烯类的骨架重组中的关键中间体）的中间体的实验证据。除了烯炔的骨架重组外，还发现Rh（II）配合物对炔烃衍生物的某些环异构化反应具有很高的催化活性，包括烯炔烃双环化为双环[4.1.0]庚烯衍生物以及炔基呋喃环化成苯酚衍生物。

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  • 来源
    《Journal of the American Chemical Society》 |2009年第42期|15203-15211|共9页
  • 作者

    Kazusa Ota; Sang Ick Lee; Jhih-Meng Tang; Manabu Takachi; Hiromi Nakai; Tsumom Morimoto; Hitoshi Sakurai; Ken Kataoka; Naoto Chatani;

  • 作者单位

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama, Ikoma, Nara 630-0192,Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

    Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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