Alkene Dicarbofunctionalization

Alkene Dicarbofunctionalization

Author: Li Grundl

Transition-metal-catalyzed vicinal dicarbofunctionalization of alkenes is a powerful tool in organic synthesis, because it can rapidly construct complex molecules from simple and readily available alkenes. However, three-component dicarbofunctionalization of alkenes with organohalides and organometallic reagents are still rare and challenging because of the side reactions.

Ramesh Giri, University of New Mexico, Albuquerque, USA, and colleagues have developed a regioselective dicarbofuncationalization of styrenes with aryl halides and arylzinc halide [1]. Keary M. Engle, Scripps Research Institute, La Jolla, CA, USA, and colleagues have also achieved a regioselective dicarbofunctionalization of terminal and internal non-conjugated alkenes with aryl or vinyl halides and diaryl or dialkyl zinc [2]. Both reactions were carried out in dioxane using Ni(cod)2 (cod = cyclooctadiene) as a catalyst.

Giri and coworkers used a removable imine as the coordinating direct group (DG, see pictured) to stabilize the intermediate before transmetalation and further avoid the side reactions [1]. Engle and coworkers used 8-aminoquinoline as the chelating direct group to achieve the same goal [2]. These methods can be very useful in synthesizing natural products and bioactive molecules.

  1. Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles,
    Bijay Shrestha, Prakash Basnet, Roshan K. Dhungana, Shekhar KC, Surendra Thapa, Jeremiah M. Sears, Ramesh Giri,
    J. Am. Chem. Soc. 2017.
    DOI: 10.1021/jacs.7b06340
  2. Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling,
    Joseph Derosa, Van T. Tran, Mark N. Boulous, Jason S. Chen, Keary M. Engle,
    J. Am. Chem. Soc. 2017.
    DOI: 10.1021/jacs.7b06567


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