PtBr2-catalyzed transformation of allyl(o-ethynylaryl)carbinol derivatives into functionalized indenes. Formal sp3 C-H bond activation

Gan B. Bajracharya; Nirmal K. Pahadi; Ilya D. Gridnev; Yoshinori Yamamoto

doi:10.1021/jo060951g

PtBr₂-catalyzed transformation of allyl(o-ethynylaryl)carbinol derivatives into functionalized indenes. Formal sp³ C-H bond activation

Gan B. Bajracharya, Nirmal K. Pahadi, Ilya D. Gridnev, Yoshinori Yamamoto

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

94 Citations (Scopus)

Abstract

The PtBr₂-catalyzed reaction of 1-ethynyl-2-(1-alkoxybut-3-enyl) benzenes at 120 °C in CH₃CN gave functionalized indenes in good to allowable yields. Most probably, the hydrogen at the terminal alkyne is transferred to the adjacent internal β-carbon to form an (η²-vinylidene)platinum carbene intermediate, which activates the sp³ C-H bond at the benzylic carbon. This reaction pathway is supported by DFT calculations which suggest that the formation of the Pt-vinylidene complex is the rate-limiting stage for the whole transformation.

Original language	English
Pages (from-to)	6204-6210
Number of pages	7
Journal	Journal of Organic Chemistry
Volume	71
Issue number	16
DOIs	https://doi.org/10.1021/jo060951g
Publication status	Published - 2006 Aug 1

ASJC Scopus subject areas

Organic Chemistry

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title = "PtBr2-catalyzed transformation of allyl(o-ethynylaryl)carbinol derivatives into functionalized indenes. Formal sp3 C-H bond activation",

abstract = "The PtBr2-catalyzed reaction of 1-ethynyl-2-(1-alkoxybut-3-enyl) benzenes at 120 °C in CH3CN gave functionalized indenes in good to allowable yields. Most probably, the hydrogen at the terminal alkyne is transferred to the adjacent internal β-carbon to form an (η2-vinylidene)platinum carbene intermediate, which activates the sp3 C-H bond at the benzylic carbon. This reaction pathway is supported by DFT calculations which suggest that the formation of the Pt-vinylidene complex is the rate-limiting stage for the whole transformation.",

author = "Bajracharya, {Gan B.} and Pahadi, {Nirmal K.} and Gridnev, {Ilya D.} and Yoshinori Yamamoto",

year = "2006",

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T1 - PtBr2-catalyzed transformation of allyl(o-ethynylaryl)carbinol derivatives into functionalized indenes. Formal sp3 C-H bond activation

AU - Bajracharya, Gan B.

AU - Pahadi, Nirmal K.

AU - Gridnev, Ilya D.

AU - Yamamoto, Yoshinori

PY - 2006/8/1

Y1 - 2006/8/1

N2 - The PtBr2-catalyzed reaction of 1-ethynyl-2-(1-alkoxybut-3-enyl) benzenes at 120 °C in CH3CN gave functionalized indenes in good to allowable yields. Most probably, the hydrogen at the terminal alkyne is transferred to the adjacent internal β-carbon to form an (η2-vinylidene)platinum carbene intermediate, which activates the sp3 C-H bond at the benzylic carbon. This reaction pathway is supported by DFT calculations which suggest that the formation of the Pt-vinylidene complex is the rate-limiting stage for the whole transformation.

AB - The PtBr2-catalyzed reaction of 1-ethynyl-2-(1-alkoxybut-3-enyl) benzenes at 120 °C in CH3CN gave functionalized indenes in good to allowable yields. Most probably, the hydrogen at the terminal alkyne is transferred to the adjacent internal β-carbon to form an (η2-vinylidene)platinum carbene intermediate, which activates the sp3 C-H bond at the benzylic carbon. This reaction pathway is supported by DFT calculations which suggest that the formation of the Pt-vinylidene complex is the rate-limiting stage for the whole transformation.

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PtBr₂-catalyzed transformation of allyl(o-ethynylaryl)carbinol derivatives into functionalized indenes. Formal sp³ C-H bond activation

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