Selectivity switch in the synthesis of vinylgold(I) intermediates

A. Stephen K Hashmi; Andreas M. Schuster; Sylvain Gaillard; Luigi Cavallo; Albert Poater; Steven P. Nolan

doi:10.1021/om2009556

Selectivity switch in the synthesis of vinylgold(I) intermediates

A. Stephen K Hashmi, Andreas M. Schuster, Sylvain Gaillard, Luigi Cavallo, Albert Poater, Steven P. Nolan

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

111 Scopus citations

Abstract

An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.

Original language	English (US)
Pages (from-to)	6328-6337
Number of pages	10
Journal	Organometallics
Volume	30
Issue number	22
DOIs	https://doi.org/10.1021/om2009556
State	Published - Nov 28 2011

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The ERC (FUNCAT to SPN) and the EPSRC are gratefully acknowledged for support of this work. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-04170). Umicore AG and Chemetall AG are thanked for their generous gifts of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder. We thank Dr. Pierrick Nun for valuable discussions.

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Selectivity switch in the synthesis of vinylgold(I) intermediates",

abstract = "An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected {"}selectivity switch{"} for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with {"}classical{"} I activation of the alkyne framework of the carboxamides, and the second represents an {"}unusual{"} use of the basic Br{\o}nsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. {\textcopyright} 2011 American Chemical Society.",

author = "Hashmi, {A. Stephen K} and Schuster, {Andreas M.} and Sylvain Gaillard and Luigi Cavallo and Albert Poater and Nolan, {Steven P.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The ERC (FUNCAT to SPN) and the EPSRC are gratefully acknowledged for support of this work. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-04170). Umicore AG and Chemetall AG are thanked for their generous gifts of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder. We thank Dr. Pierrick Nun for valuable discussions.",

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AU - Hashmi, A. Stephen K

AU - Schuster, Andreas M.

AU - Gaillard, Sylvain

AU - Cavallo, Luigi

AU - Poater, Albert

AU - Nolan, Steven P.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The ERC (FUNCAT to SPN) and the EPSRC are gratefully acknowledged for support of this work. A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-04170). Umicore AG and Chemetall AG are thanked for their generous gifts of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder. We thank Dr. Pierrick Nun for valuable discussions.

PY - 2011/11/28

Y1 - 2011/11/28

N2 - An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.

AB - An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)]+ species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)]+ species with "classical" I activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Brønsted character of [Au(IPr)(OH)]. Mechanistic and DFT studies support the mechanistic hypotheses. © 2011 American Chemical Society.

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Selectivity switch in the synthesis of vinylgold(I) intermediates

Abstract

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