A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

Kane A. C. Bastick; Allan J. B. Watson

doi:10.1021/acscatal.3c00921

A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

Kane A. C. Bastick, Allan J. B. Watson^*

^*Corresponding author for this work

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

6 Citations (Scopus)

15 Downloads (Pure)

Abstract

A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C₁ insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp³)–C(sp²) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.

Original language	English
Pages (from-to)	7013–7018
Number of pages	6
Journal	ACS Catalysis
Volume	13
Issue number	10
Early online date	9 May 2023
DOIs	https://doi.org/10.1021/acscatal.3c00921
Publication status	Published - 19 May 2023

Keywords

Boron
Catalysis
Chemoselectivity
Cross-coupling
Homologation
Palladium

Access to Document

10.1021/acscatal.3c00921Licence: CC BY

Bastick_2023_ACS-C_Pd-catalyzed_CC
Copyright © 2023 The Authors. Published by American Chemical Society. This is an open access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.8 MBLicence: CC BY

A biochemical boron tagging stategy: A biochemical boron tagging strategy for biomolecule visualisation and profiling
Watson, A. J. B. (PI)
The Leverhulme Trust
1/09/22 → 31/08/24
Project: Fellowship
Chemoselective cross-coupling: Chemoselective cross-coupling via control of anion metathesis at Pd(II)
Watson, A. J. B. (PI)
EPSRC
1/07/18 → 31/08/22
Project: Standard

On the discovery and applications of a palladium-catalysed organoboron homologation (Thesis Data)
Bastick, K. A. C. (Creator) & Watson, A. J. B. (Supervisor), University of St Andrews, 9 May 2024
DOI: 10.17630/c856da65-6df8-4840-9f7c-1d935f0377a7, https://doi.org/10.17630/sta/895
Dataset: Thesis dataset

File
A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation (dataset)
Watson, A. J. B. (Creator), University of St Andrews, 24 May 2023
DOI: 10.17630/846ed836-c5ff-4927-82cb-3ed6648bf69b
Dataset

File

Cite this

@article{83b92b3ee00e49e584a93dee314c78c7,

title = "A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation",

abstract = "A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)–C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.",

keywords = "Boron, Catalysis, Chemoselectivity, Cross-coupling, Homologation, Palladium",

author = "Bastick, {Kane A. C.} and Watson, {Allan J. B.}",

note = "Funding: K.A.C.B. thanks EPSRC and the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship (RF-2022-014) and the EPSRC Programme Grant “Boron: Beyond the Reagent” (EP/W007517) for support.",

year = "2023",

month = may,

day = "19",

doi = "10.1021/acscatal.3c00921",

language = "English",

volume = "13",

pages = "7013–7018",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society (ACS)",

number = "10",

}

TY - JOUR

T1 - A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

AU - Bastick, Kane A. C.

AU - Watson, Allan J. B.

N1 - Funding: K.A.C.B. thanks EPSRC and the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship (RF-2022-014) and the EPSRC Programme Grant “Boron: Beyond the Reagent” (EP/W007517) for support.

PY - 2023/5/19

Y1 - 2023/5/19

N2 - A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)–C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.

AB - A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)–C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.

KW - Boron

KW - Catalysis

KW - Chemoselectivity

KW - Cross-coupling

KW - Homologation

KW - Palladium

U2 - 10.1021/acscatal.3c00921

DO - 10.1021/acscatal.3c00921

M3 - Article

SN - 2155-5435

VL - 13

SP - 7013

EP - 7018

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

Abstract

Keywords

Access to Document

Fingerprint

Projects

A biochemical boron tagging stategy: A biochemical boron tagging strategy for biomolecule visualisation and profiling

Chemoselective cross-coupling: Chemoselective cross-coupling via control of anion metathesis at Pd(II)

Datasets

On the discovery and applications of a palladium-catalysed organoboron homologation (Thesis Data)

A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation (dataset)

Cite this