Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation

Juana M Pérez; Roxana Postolache; Marta Castiñeira Reis; Esther G. Sinnema; Denisa Vargová; Folkert de Vries; Edwin Otten; Luo Ge; Syuzanna R Harutyunyan

doi:10.1021/jacs.1c10756

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation

Juana M Pérez, Roxana Postolache, Marta Castiñeira Reis, Esther G. Sinnema, Denisa Vargová, Folkert de Vries, Edwin Otten, Luo Ge^*, Syuzanna R Harutyunyan^*

^*Corresponding author for this work

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

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Abstract

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

Original language	English
Pages (from-to)	20071–20076
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	143
Issue number	48
Early online date	19-Nov-2021
DOIs	https://doi.org/10.1021/jacs.1c10756
Publication status	Published - 8-Dec-2021

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10.1021/jacs.1c10756Licence: CC BY-NC-ND

Manganese(I)-Catalyzed H−P Bond Activation via Metal−Ligand CooperationFinal publisher's version, 1.71 MBLicence: CC BY-NC-ND

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CCDC 2085290: Experimental Crystal Structure Determination
Pérez Galera, J. (Contributor), Postolache, R. (Contributor), Castiñeira Reis, M. (Contributor), Sinnema, E. (Contributor), Vargová, D. (Contributor), de Vries, F. (Contributor), Otten, E. (Contributor), Ge, L. (Contributor) & Harutyunyan, S. (Contributor), The Cambridge Structural Database, 22-May-2021
DOI: 10.5517/ccdc.csd.cc27zxfl, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc27zxfl&sid=DataCite
Dataset
CCDC 2085460: Experimental Crystal Structure Determination
Pérez Galera, J. (Contributor), Postolache, R. (Contributor), Castiñeira Reis, M. (Contributor), Sinnema, E. (Contributor), Vargová, D. (Contributor), de Vries, F. (Contributor), Otten, E. (Contributor), Ge, L. (Contributor) & Harutyunyan, S. (Contributor), The Cambridge Structural Database, 23-May-2021
DOI: 10.5517/ccdc.csd.cc2802x9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2802x9&sid=DataCite
Dataset
CCDC 2120248: Experimental Crystal Structure Determination
Pérez Galera, J. (Contributor), Postolache, R. (Contributor), Castiñeira Reis, M. (Contributor), Sinnema, E. (Contributor), Vargová, D. (Contributor), de Vries, F. (Contributor), Otten, E. (Contributor), Ge, L. (Contributor) & Harutyunyan, S. (Contributor), The Cambridge Structural Database, 4-Nov-2021
DOI: 10.5517/ccdc.csd.cc29593x, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc29593x&sid=DataCite
Dataset

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@article{f69aebef09024c2f860adab29d487a05,

title = "Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation",

abstract = "Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.",

author = "P{\'e}rez, {Juana M} and Roxana Postolache and {Casti{\~n}eira Reis}, Marta and Sinnema, {Esther G.} and Denisa Vargov{\'a} and {de Vries}, Folkert and Edwin Otten and Luo Ge and Harutyunyan, {Syuzanna R}",

year = "2021",

month = dec,

day = "8",

doi = "10.1021/jacs.1c10756",

language = "English",

volume = "143",

pages = "20071–20076",

journal = "Journal of the American Chemical Society",

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T1 - Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation

AU - Pérez, Juana M

AU - Postolache, Roxana

AU - Castiñeira Reis, Marta

AU - Sinnema, Esther G.

AU - Vargová, Denisa

AU - de Vries, Folkert

AU - Otten, Edwin

AU - Ge, Luo

AU - Harutyunyan, Syuzanna R

PY - 2021/12/8

Y1 - 2021/12/8

N2 - Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

AB - Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

U2 - 10.1021/jacs.1c10756

DO - 10.1021/jacs.1c10756

M3 - Article

C2 - 34797634

SN - 0002-7863

VL - 143

SP - 20071

EP - 20076

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 48

ER -

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation

Abstract

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Datasets

CCDC 2085290: Experimental Crystal Structure Determination

CCDC 2085460: Experimental Crystal Structure Determination

CCDC 2120248: Experimental Crystal Structure Determination

Cite this