Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

Alberto Gómez-Herrera; Fady Nahra; Marcel Brill; Steven P. Nolan; Catherine S. J. Cazin

doi:10.1002/cctc.201600868

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

Alberto Gómez-Herrera, Fady Nahra, Marcel Brill, Steven P. Nolan, Catherine S. J. Cazin

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

35 Scopus citations

Abstract

The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

Original language	English (US)
Pages (from-to)	3381-3388
Number of pages	8
Journal	ChemCatChem
Volume	8
Issue number	21
DOIs	https://doi.org/10.1002/cctc.201600868
State	Published - Sep 26 2016
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): OSR-2015-CCF-1974–03
Acknowledgements: The authors gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), Syngenta (studentship to A.G.H.), King Saud University (S.P.N.) and the EPSRC (EP/K503162/1) for funding. We are also grateful to Umicore for the loan of Pd complexes and to the EPSRC National Mass Spectrometry Service Centre at Swansea University for HRMS analyses. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974–03.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1002/cctc.201600868

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title = "Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes",

abstract = "The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.",

author = "Alberto G{\'o}mez-Herrera and Fady Nahra and Marcel Brill and Nolan, {Steven P.} and Cazin, {Catherine S. J.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): OSR-2015-CCF-1974–03 Acknowledgements: The authors gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), Syngenta (studentship to A.G.H.), King Saud University (S.P.N.) and the EPSRC (EP/K503162/1) for funding. We are also grateful to Umicore for the loan of Pd complexes and to the EPSRC National Mass Spectrometry Service Centre at Swansea University for HRMS analyses. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974–03. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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AU - Nahra, Fady

AU - Brill, Marcel

AU - Nolan, Steven P.

AU - Cazin, Catherine S. J.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): OSR-2015-CCF-1974–03 Acknowledgements: The authors gratefully acknowledge the Royal Society (University Research Fellowship to C.S.J.C.), Syngenta (studentship to A.G.H.), King Saud University (S.P.N.) and the EPSRC (EP/K503162/1) for funding. We are also grateful to Umicore for the loan of Pd complexes and to the EPSRC National Mass Spectrometry Service Centre at Swansea University for HRMS analyses. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974–03. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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N2 - The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

AB - The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

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DO - 10.1002/cctc.201600868

M3 - Article

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VL - 8

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JO - ChemCatChem

JF - ChemCatChem

IS - 21

ER -

Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

Abstract

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