Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

Jian Zhou; Ling Meng; Shujuan Lin; Baohua Cai; Jun (Joelle) Wang

doi:10.1002/anie.202303727

Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

Jian Zhou, Ling Meng, Shujuan Lin, Baohua Cai, Jun (Joelle) Wang^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

26 Citations (Scopus)

Abstract

Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.

Original language	English
Article number	e202303727
Number of pages	8
Journal	Angewandte Chemie. International Edition
Volume	62
Issue number	26
Early online date	25 Apr 2023
DOIs	https://doi.org/10.1002/anie.202303727
Publication status	Published - 26 Jun 2023

Scopus Subject Areas

General Chemistry
Catalysis

User-Defined Keywords

C−C Bond Cleavage
C−P Bond Formation
DFT Calculations
Hydrophosphinylation
Phosphine

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10.1002/anie.202303727

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title = "Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes",

abstract = "Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.",

keywords = "C−C Bond Cleavage, C−P Bond Formation, DFT Calculations, Hydrophosphinylation, Phosphine",

author = "Jian Zhou and Ling Meng and Shujuan Lin and Baohua Cai and Wang, {Jun (Joelle)}",

note = "Funding Information: We gratefully acknowledge the Research Grants Council of Hong Kong (GRF 12303422), and National Natural Science Foundation of China (NSFC 22271241), HKBU RC‐Tier 2 Start‐up Grant and KRPS grant for financial support. Dr. Xiaoyong Chang from SUSTech is gratefully acknowledged for X‐ray crystallographic analysis. Publisher Copyright: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

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doi = "10.1002/anie.202303727",

language = "English",

volume = "62",

journal = "Angewandte Chemie. International Edition",

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TY - JOUR

T1 - Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

AU - Zhou, Jian

AU - Meng, Ling

AU - Lin, Shujuan

AU - Cai, Baohua

AU - Wang, Jun (Joelle)

N1 - Funding Information: We gratefully acknowledge the Research Grants Council of Hong Kong (GRF 12303422), and National Natural Science Foundation of China (NSFC 22271241), HKBU RC‐Tier 2 Start‐up Grant and KRPS grant for financial support. Dr. Xiaoyong Chang from SUSTech is gratefully acknowledged for X‐ray crystallographic analysis. Publisher Copyright: © 2023 Wiley-VCH GmbH.

PY - 2023/6/26

Y1 - 2023/6/26

N2 - Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.

AB - Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C−C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.

KW - C−C Bond Cleavage

KW - C−P Bond Formation

KW - DFT Calculations

KW - Hydrophosphinylation

KW - Phosphine

UR - http://www.scopus.com/inward/record.url?scp=85159319481&partnerID=8YFLogxK

U2 - 10.1002/anie.202303727

DO - 10.1002/anie.202303727

M3 - Journal article

SN - 1433-7851

VL - 62

JO - Angewandte Chemie. International Edition

JF - Angewandte Chemie. International Edition

IS - 26

M1 - e202303727

ER -

Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes

Abstract

Scopus Subject Areas

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