Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters

Timothy P. Aldhous; Raymond Chung; Abbas Hassan; Andrew G. Dalling; Phillippa Cooper; Simon Grélaud; Richard J. Mudd; Lyman J. Feron; Paul D. Kemmitt; John F. Bower

doi:10.1002/anie.202502569

Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters

Timothy P. Aldhous
, Raymond Chung
, Abbas Hassan
, Andrew G. Dalling
, Phillippa Cooper
, Simon Grélaud
, Richard J. Mudd
, Lyman J. Feron
, Paul D. Kemmitt
, John F. Bower^*

^*Corresponding author for this work

School of Chemistry

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

13 Citations (Scopus)

Abstract

Ir‐systems modified with ferrocene‐based homochiral diphosphonite ligands, prepared from functionalized SPINOL derivatives, promote benzamide‐directed hydroarylative cross‐couplings involving minimally activated alkenes. The processes are highly branched selective and enantioselective. Accordingly, tertiary benzylic stereocenters are generated under byproduct‐free conditions. This contrast with conventional cross‐coupling approaches, which are less step and atom economical. Preliminary results show that the process extends to the formation of quaternary benzylic stereocenters.

Original language	English
Article number	e202502569
Number of pages	9
Journal	Angewandte Chemie International Edition
Volume	64
Issue number	22
Early online date	30 Mar 2025
DOIs	https://doi.org/10.1002/anie.202502569
Publication status	E-pub ahead of print - 30 Mar 2025

Bibliographical note

Publisher Copyright:
© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

Alkene
Enantioselective
Hydroarylation
Cross‐coupling
Iridium

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Aldhous, T. P., Chung, R., Hassan, A., Dalling, A. G., Cooper, P., Grélaud, S., Mudd, R. J., Feron, L. J., Kemmitt, P. D., & Bower, J. F. (2025). Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters. Angewandte Chemie International Edition, 64(22), Article e202502569. Advance online publication. https://doi.org/10.1002/anie.202502569

@article{5fff850414d84b75b0371058769d22e7,

title = "Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters",

abstract = "Ir‐systems modified with ferrocene‐based homochiral diphosphonite ligands, prepared from functionalized SPINOL derivatives, promote benzamide‐directed hydroarylative cross‐couplings involving minimally activated alkenes. The processes are highly branched selective and enantioselective. Accordingly, tertiary benzylic stereocenters are generated under byproduct‐free conditions. This contrast with conventional cross‐coupling approaches, which are less step and atom economical. Preliminary results show that the process extends to the formation of quaternary benzylic stereocenters.",

keywords = "Alkene, Enantioselective, Hydroarylation, Cross‐coupling, Iridium",

author = "Aldhous, \{Timothy P.\} and Raymond Chung and Abbas Hassan and Dalling, \{Andrew G.\} and Phillippa Cooper and Simon Gr{\'e}laud and Mudd, \{Richard J.\} and Feron, \{Lyman J.\} and Kemmitt, \{Paul D.\} and Bower, \{John F.\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2025",

month = mar,

day = "30",

doi = "10.1002/anie.202502569",

language = "English",

volume = "64",

journal = "Angewandte Chemie International Edition",

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Aldhous, TP, Chung, R, Hassan, A, Dalling, AG, Cooper, P, Grélaud, S, Mudd, RJ, Feron, LJ, Kemmitt, PD & Bower, JF 2025, 'Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters', Angewandte Chemie International Edition, vol. 64, no. 22, e202502569. https://doi.org/10.1002/anie.202502569

Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters. / Aldhous, Timothy P.; Chung, Raymond; Hassan, Abbas et al.
In: Angewandte Chemie International Edition, Vol. 64, No. 22, e202502569, 30.03.2025.

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

TY - JOUR

T1 - Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters

AU - Aldhous, Timothy P.

AU - Chung, Raymond

AU - Hassan, Abbas

AU - Dalling, Andrew G.

AU - Cooper, Phillippa

AU - Grélaud, Simon

AU - Mudd, Richard J.

AU - Feron, Lyman J.

AU - Kemmitt, Paul D.

AU - Bower, John F.

PY - 2025/3/30

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N2 - Ir‐systems modified with ferrocene‐based homochiral diphosphonite ligands, prepared from functionalized SPINOL derivatives, promote benzamide‐directed hydroarylative cross‐couplings involving minimally activated alkenes. The processes are highly branched selective and enantioselective. Accordingly, tertiary benzylic stereocenters are generated under byproduct‐free conditions. This contrast with conventional cross‐coupling approaches, which are less step and atom economical. Preliminary results show that the process extends to the formation of quaternary benzylic stereocenters.

AB - Ir‐systems modified with ferrocene‐based homochiral diphosphonite ligands, prepared from functionalized SPINOL derivatives, promote benzamide‐directed hydroarylative cross‐couplings involving minimally activated alkenes. The processes are highly branched selective and enantioselective. Accordingly, tertiary benzylic stereocenters are generated under byproduct‐free conditions. This contrast with conventional cross‐coupling approaches, which are less step and atom economical. Preliminary results show that the process extends to the formation of quaternary benzylic stereocenters.

KW - Alkene

KW - Enantioselective

KW - Hydroarylation

KW - Cross‐coupling

KW - Iridium

U2 - 10.1002/anie.202502569

DO - 10.1002/anie.202502569

M3 - Article (Academic Journal)

C2 - 40111756

SN - 1433-7851

VL - 64

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 22

M1 - e202502569

ER -

Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters

Abstract

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Keywords

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