An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections

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  • Niels Hammer
  • ,
  • Mette Louise Christensen
  • Yu Chen, Nanjing University
  • ,
  • Daniel Naharro, Aarhus University, Aarhus, Denmark.
  • ,
  • Fang Liu, Nanjing Agricultural University
  • ,
  • Karl Anker Jørgensen
  • K. N. Houk, University California Los Angeles

We report an experimental discovery and computational investigation of the first photochemical stereoselective [1,3]-sigmatropic silyl shift of an allylsilane. An organocatalytic enantioselective cascade annulation generates a trimethylsilyl-o-isotoluene reactant in >99:1 e.r., and this trimethylsilyl-o-isotoluene contains an allylic silane moiety that undergoes a stereoselective photochemical [1,3]-silyl shift to form a benzylsilane with 96:4 e.r. The mechanism of this unprecedented [1,3]-silyl shift has been elucidated by a series of experimental studies and CASSCF, DFT, and TD-DFT calculations on model systems and the experimental system. The highly stereoselective photoreaction is proposed to occur via a singlet silyl/allyl conical intersection. This is a new demonstration of the role of conical intersections in selective photochemistry.

OriginalsprogEngelsk
TidsskriftJournal of the American Chemical Society
Vol/bind142
Nummer13
Sider (fra-til)6030-6035
Antal sider6
ISSN0002-7863
DOI
StatusUdgivet - 2020

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