Steric influence on reactions of benzyl potassium species with CO

Tongtong Wang; Maotong Xu; Andrew R. Jupp; Zheng‐Wang Qu; Stefan Grimme; Douglas W. Stephan

doi:10.1002/asia.202101127

Steric influence on reactions of benzyl potassium species with CO

Tongtong Wang, Maotong Xu, Andrew R. Jupp, Zheng‐Wang Qu, Stefan Grimme, Douglas W. Stephan

Chemistry

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Abstract

Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph ₃SiO)(PhCH ₂)C) ₂ 2 and PhCH ₂C(O)CH(OH)CH ₂Ph 3. Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu ₂C ₆H ₂(C(OSiR ₃)C(OSiR ₃)CH ₂) (R=Me 6, Ph 7). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu ₂C ₆H ₃) ₃C ₆H ₂CH ₂C(O)) ₂ 15.

Original language	English
Pages (from-to)	3640-3644
Journal	Chemistry – An Asian Journal
Volume	16
Issue number	22
Early online date	30 Sept 2021
DOIs	https://doi.org/10.1002/asia.202101127
Publication status	E-pub ahead of print - 30 Sept 2021

Bibliographical note

Funding Information:
D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Killam Foundation and the RSC(UK) are thanked for a Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (project SPP1807) for financial support. A.R.J. is grateful for a Banting Postdoctoral Fellowship for funding. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. Dr. K. Demmans is thanked for collection of EPR spectra. Open Access funding enabled and organized by Projekt DEAL.

Keywords

C−C bond formation
carbene
carbon monoxide
radical
tropolone

ASJC Scopus subject areas

Biochemistry
Organic Chemistry

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10.1002/asia.202101127

WangT2021StericFinal published version, 1.72 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

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title = "Steric influence on reactions of benzyl potassium species with CO",

abstract = "Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph 3SiO)(PhCH 2)C) 2 2 and PhCH 2C(O)CH(OH)CH 2Ph 3. Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu 2C 6H 2(C(OSiR 3)C(OSiR 3)CH 2) (R=Me 6, Ph 7). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu 2C 6H 3) 3C 6H 2CH 2C(O)) 2 15. ",

keywords = "C−C bond formation, carbene, carbon monoxide, radical, tropolone",

author = "Tongtong Wang and Maotong Xu and Jupp, {Andrew R.} and Zheng‐Wang Qu and Stefan Grimme and Stephan, {Douglas W.}",

note = "Funding Information: D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Killam Foundation and the RSC(UK) are thanked for a Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (project SPP1807) for financial support. A.R.J. is grateful for a Banting Postdoctoral Fellowship for funding. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. Dr. K. Demmans is thanked for collection of EPR spectra. Open Access funding enabled and organized by Projekt DEAL.",

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AU - Wang, Tongtong

AU - Xu, Maotong

AU - Jupp, Andrew R.

AU - Qu, Zheng‐Wang

AU - Grimme, Stefan

AU - Stephan, Douglas W.

N1 - Funding Information: D.W.S. is grateful to NSERC of Canada for research support and the award of a Canada Research Chair. The Guggenheim Foundation, the Killam Foundation and the RSC(UK) are thanked for a Guggenheim fellowship, a 2021 Killam Prize and a 2021 Centenary Prize, respectively. S.G and Z.W.Q are grateful to DFG (project SPP1807) for financial support. A.R.J. is grateful for a Banting Postdoctoral Fellowship for funding. M.X is grateful for the award of C.H. Bayley Scholarship. T.W. is grateful to China Scholarship Council for financial support. Dr. K. Demmans is thanked for collection of EPR spectra. Open Access funding enabled and organized by Projekt DEAL.

PY - 2021/9/30

Y1 - 2021/9/30

N2 - Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph 3SiO)(PhCH 2)C) 2 2 and PhCH 2C(O)CH(OH)CH 2Ph 3. Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu 2C 6H 2(C(OSiR 3)C(OSiR 3)CH 2) (R=Me 6, Ph 7). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu 2C 6H 3) 3C 6H 2CH 2C(O)) 2 15.

AB - Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph 3SiO)(PhCH 2)C) 2 2 and PhCH 2C(O)CH(OH)CH 2Ph 3. Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu 2C 6H 2(C(OSiR 3)C(OSiR 3)CH 2) (R=Me 6, Ph 7). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu 2C 6H 3) 3C 6H 2CH 2C(O)) 2 15.

KW - C−C bond formation

KW - carbene

KW - carbon monoxide

KW - radical

KW - tropolone

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IS - 22

ER -

Steric influence on reactions of benzyl potassium species with CO

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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