Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups

Xiao Yang Chen; Erik J. Sorensen

doi:10.1021/jacs.8b00048

Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups

Xiao Yang Chen, Erik J. Sorensen

Chemistry

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

115 Scopus citations

Abstract

The direct, Pd-catalyzed ortho C-H methylation and fluorination of benzaldehydes have been accomplished using commercially available orthanilic acids as transient directing groups. In these reactions, the 1-fluoro-2,4,6-trimethylpyridinium salts can be either a bystanding F⁺ oxidant or an electrophilic fluorinating reagent. An X-ray crystal structure of a benzaldehyde ortho C-H palladation intermediate was obtained using triphenylphosphine as the stabilizing ligand.

Original language	English (US)
Pages (from-to)	2789-2792
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	140
Issue number	8
DOIs	https://doi.org/10.1021/jacs.8b00048
State	Published - Feb 28 2018

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.8b00048

Cite this

@article{fb41fc50a87b477d8447f20b8f09050a,

title = "Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups",

abstract = "The direct, Pd-catalyzed ortho C-H methylation and fluorination of benzaldehydes have been accomplished using commercially available orthanilic acids as transient directing groups. In these reactions, the 1-fluoro-2,4,6-trimethylpyridinium salts can be either a bystanding F+ oxidant or an electrophilic fluorinating reagent. An X-ray crystal structure of a benzaldehyde ortho C-H palladation intermediate was obtained using triphenylphosphine as the stabilizing ligand.",

author = "Chen, {Xiao Yang} and Sorensen, {Erik J.}",

note = "Funding Information: We acknowledge Prof. Jin-Quan Yu at the Scripps Research Institute for his advice on obtaining single crystals of the palladacycle intermediate. We also thank John Eng and Phil Jeffrey at Princeton University for their technical assistance with our mass spectrometric and X-ray crystallographic analyses. This work was supported by NSF under the CCI Center for Selective C−H Functionalization (CHE-1700982) and Princeton University.",

year = "2018",

month = feb,

day = "28",

doi = "10.1021/jacs.8b00048",

language = "English (US)",

volume = "140",

pages = "2789--2792",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups

AU - Chen, Xiao Yang

AU - Sorensen, Erik J.

N1 - Funding Information: We acknowledge Prof. Jin-Quan Yu at the Scripps Research Institute for his advice on obtaining single crystals of the palladacycle intermediate. We also thank John Eng and Phil Jeffrey at Princeton University for their technical assistance with our mass spectrometric and X-ray crystallographic analyses. This work was supported by NSF under the CCI Center for Selective C−H Functionalization (CHE-1700982) and Princeton University.

PY - 2018/2/28

Y1 - 2018/2/28

N2 - The direct, Pd-catalyzed ortho C-H methylation and fluorination of benzaldehydes have been accomplished using commercially available orthanilic acids as transient directing groups. In these reactions, the 1-fluoro-2,4,6-trimethylpyridinium salts can be either a bystanding F+ oxidant or an electrophilic fluorinating reagent. An X-ray crystal structure of a benzaldehyde ortho C-H palladation intermediate was obtained using triphenylphosphine as the stabilizing ligand.

AB - The direct, Pd-catalyzed ortho C-H methylation and fluorination of benzaldehydes have been accomplished using commercially available orthanilic acids as transient directing groups. In these reactions, the 1-fluoro-2,4,6-trimethylpyridinium salts can be either a bystanding F+ oxidant or an electrophilic fluorinating reagent. An X-ray crystal structure of a benzaldehyde ortho C-H palladation intermediate was obtained using triphenylphosphine as the stabilizing ligand.

UR - http://www.scopus.com/inward/record.url?scp=85042724226&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042724226&partnerID=8YFLogxK

U2 - 10.1021/jacs.8b00048

DO - 10.1021/jacs.8b00048

M3 - Article

C2 - 29412651

AN - SCOPUS:85042724226

SN - 0002-7863

VL - 140

SP - 2789

EP - 2792

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 8

ER -

Pd-Catalyzed, ortho C-H Methylation and Fluorination of Benzaldehydes Using Orthanilic Acids as Transient Directing Groups

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this