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

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An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections. / Hammer, Niels; Christensen, Mette Louise; Chen, Yu; Naharro, Daniel; Liu, Fang; Jørgensen, Karl Anker; Houk, K. N.

I: Journal of the American Chemical Society, Bind 142, Nr. 13, 2020, s. 6030-6035.

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avisTidsskriftartikelForskningpeer review

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Hammer, N, Christensen, ML, Chen, Y, Naharro, D, Liu, F, Jørgensen, KA & Houk, KN 2020, 'An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections', Journal of the American Chemical Society, bind 142, nr. 13, s. 6030-6035. https://doi.org/10.1021/jacs.9b11579

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Author

Hammer, Niels ; Christensen, Mette Louise ; Chen, Yu ; Naharro, Daniel ; Liu, Fang ; Jørgensen, Karl Anker ; Houk, K. N. / An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections. I: Journal of the American Chemical Society. 2020 ; Bind 142, Nr. 13. s. 6030-6035.

Bibtex

@article{68cc5543f705439995e1eb2e95fa08b8,
title = "An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections",
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.",
author = "Niels Hammer and Christensen, {Mette Louise} and Yu Chen and Daniel Naharro and Fang Liu and J{\o}rgensen, {Karl Anker} and Houk, {K. N.}",
year = "2020",
doi = "10.1021/jacs.9b11579",
language = "English",
volume = "142",
pages = "6030--6035",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "ACS Publications",
number = "13",

}

RIS

TY - JOUR

T1 - An Experimental Stereoselective Photochemical [1s,3s]-Sigmatropic Silyl Shift and the Existence of Silyl/Allyl Conical Intersections

AU - Hammer, Niels

AU - Christensen, Mette Louise

AU - Chen, Yu

AU - Naharro, Daniel

AU - Liu, Fang

AU - Jørgensen, Karl Anker

AU - Houk, K. N.

PY - 2020

Y1 - 2020

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85082194329&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b11579

DO - 10.1021/jacs.9b11579

M3 - Journal article

C2 - 32191462

AN - SCOPUS:85082194329

VL - 142

SP - 6030

EP - 6035

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 13

ER -