铑催化的丙二烯与炔烃的交叉环三聚化和二聚化。
Rhodium-Catalyzed Cross-Cyclotrimerization and Dimerization of Allenes with Alkynes.
机构信息
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan.
出版信息
Angew Chem Int Ed Engl. 2016 Jun 1;55(23):6753-7. doi: 10.1002/anie.201602155. Epub 2016 Apr 25.
It has been established that a cationic rhodium(I)/binap complex catalyzes the cross-cyclotrimerization of two molecules of a monosubstituted allene with one molecule of a functionalized alkyne to give 3,6-dialkylidenecyclohex-1-enes. In contrast, the reactions involving di- or trisubstituted allenes and/or unfunctionalized alkynes afforded cross-dimerization products, substituted dendralenes, through β-hydrogen elimination from the corresponding rhodacycles.
已经确定，阳离子铑（I）/联萘膦络合物催化两个单取代烯丙基与一个官能化炔烃的交叉环三聚反应，生成 3,6-二亚烷基环己-1-烯。相比之下，涉及二取代或三取代烯丙基和/或非官能化炔烃的反应通过相应的铑环中的β-氢消除，生成交叉二聚化产物，取代的树枝烯。
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