Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation

Rajesh Kancherla; Krishnamoorthy Muralirajan; Bholanath Maity; Chen Zhu; Patricia E. Krach; Luigi Cavallo; Magnus Rueping

doi:10.1002/anie.201811439

Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation

Rajesh Kancherla, Krishnamoorthy Muralirajan, Bholanath Maity, Chen Zhu, Patricia E. Krach, Luigi Cavallo, Magnus Rueping

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

108 Scopus citations

Abstract

Visible-light induced, palladium catalyzed alkylations of α,β-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd is key for the efficient transformation.

Original language	English (US)
Pages (from-to)	3412-3416
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	58
Issue number	11
DOIs	https://doi.org/10.1002/anie.201811439 https://doi.org/10.1002/ange.201811439
State	Published - Jan 9 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: P.E.K. thanks the Deutsche Bundesstiftung Umwelt for a doctoral stipend. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013)/ ERC Grant Agreement no. 617044 (SunCatChem). B.M., C.Z. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for computational resources of the supercomputer Shaheen II.

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title = "Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation",

abstract = "Visible-light induced, palladium catalyzed alkylations of α,β-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd is key for the efficient transformation.",

author = "Rajesh Kancherla and Krishnamoorthy Muralirajan and Bholanath Maity and Chen Zhu and Krach, {Patricia E.} and Luigi Cavallo and Magnus Rueping",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: P.E.K. thanks the Deutsche Bundesstiftung Umwelt for a doctoral stipend. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013)/ ERC Grant Agreement no. 617044 (SunCatChem). B.M., C.Z. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for computational resources of the supercomputer Shaheen II.",

year = "2019",

month = jan,

day = "9",

doi = "10.1002/anie.201811439",

language = "English (US)",

volume = "58",

pages = "3412--3416",

journal = "Angewandte Chemie International Edition",

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T1 - Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation

AU - Kancherla, Rajesh

AU - Muralirajan, Krishnamoorthy

AU - Maity, Bholanath

AU - Zhu, Chen

AU - Krach, Patricia E.

AU - Cavallo, Luigi

AU - Rueping, Magnus

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: P.E.K. thanks the Deutsche Bundesstiftung Umwelt for a doctoral stipend. The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (FP/2007–2013)/ ERC Grant Agreement no. 617044 (SunCatChem). B.M., C.Z. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for computational resources of the supercomputer Shaheen II.

PY - 2019/1/9

Y1 - 2019/1/9

N2 - Visible-light induced, palladium catalyzed alkylations of α,β-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd is key for the efficient transformation.

AB - Visible-light induced, palladium catalyzed alkylations of α,β-unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner-sphere mechanism is operative in which a barrierless, single-electron transfer oxidative addition of the alkyl halide to Pd is key for the efficient transformation.

UR - http://hdl.handle.net/10754/631189

UR - https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201811439

UR - http://www.scopus.com/inward/record.url?scp=85059850279&partnerID=8YFLogxK

U2 - 10.1002/anie.201811439

DO - 10.1002/anie.201811439

M3 - Article

C2 - 30520235

SN - 1433-7851

VL - 58

SP - 3412

EP - 3416

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 11

ER -

Oxidative Addition to Palladium(0) Made Easy through Photoexcited-State Metal Catalysis: Experiment and Computation

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