Silylmetalation of alkenes.
Silylmetalation of alkenes is challenging due to the low reactivity of the substrates. In contrast, carbometalation of alkenes has been realized through several innovative methods, including activation of the reagent and the substrate. A similar approach could be applicable to silylmetalation of alkenes, and we have recently developed a bimetal activation method using zincate complexes for this purpose. Here, we describe how the silylzincation of alkenes was achieved. First, the strategies for carbometalation of alkenes will be summarized. Secondly, the history and development of silylzincation chemistry are briefly described. Then the details of our findings related to two types of silylzincation of alkenes, as well as recent progress in mechanistic studies, are discussed. The key point in the silylzincation of alkenes proved to be the bimetal activation of the substrate. One metal (copper or titanium) strongly coordinates and activates the alkene moiety, and the other metal (zinc) acts as the electron acceptor from the silyl group by way of the alkene moiety. This dual activation concept is expected to be applicable to other combinations of metals, as well as to new types of reactions.
Nakamura
Shinji
S
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo, Japan. uchiyama@mol.f.u-tokyo.jp
Yonehara
Mitsuhiro
M
Uchiyama
Masanobu
M
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D020058:Styrene / Q000737:chemistry; D015032:Zinc / Q000737:chemistry
D000475:Alkenes; D009942:Organometallic Compounds; D020058:Styrene; D003300:Copper; D015032:Zinc