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An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections
- Source :
- Hammer, N, Christensen, M L, Chen, Y, Naharro, D, Liu, F, Jørgensen, K A & Houk, K N 2020, ' An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections ', Journal of the American Chemical Society, vol. 142, no. 13, pp. 6030-6035 . https://doi.org/10.1021/jacs.9b11579
- Publication Year :
- 2020
-
Abstract
- 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.
Details
- ISSN :
- 15205126
- Volume :
- 142
- Issue :
- 13
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi.dedup.....f4ea5d8a9e7cf632816de3e2641e7283