Ortho-Deuteration of Aromatic Aldehydes via a Transient Directing Group-Enabled Pd-Catalyzed Hydrogen Isotope Exchange

Junhua Kong; Zhi Jiang Jiang; Jiayuan Xu; Yan Li; Hong Cao; Yanan Ding; Bencan Tang; Jia Chen; Zhanghua Gao

doi:10.1021/acs.joc.1c01411

Ortho-Deuteration of Aromatic Aldehydes via a Transient Directing Group-Enabled Pd-Catalyzed Hydrogen Isotope Exchange

Junhua Kong, Zhi Jiang Jiang, Jiayuan Xu, Yan Li, Hong Cao, Yanan Ding, Bencan Tang, Jia Chen, Zhanghua Gao

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

13 Citations (Scopus)

Abstract

A practical and scalable ortho-selective deuteration of aromatic aldehydes was accomplished by Pd-catalyzed hydrogen isotope exchange with deuterium oxide as an inexpensive deuterium source. The use of tert-leucine as a transient directing group facilitates the exchange, affording a wide range of ortho-deuterated aromatic aldehydes with deuterium incorporation up to 97%. The control experiments suggest that the addition of silver trifluoroacetate resists the unexpected reduction of Pd(II), while the theoretical study indicates a rapid reversible concerted metalation-deprotonation process.

Original language	English
Pages (from-to)	13350-13359
Number of pages	10
Journal	Journal of Organic Chemistry
Volume	86
Issue number	19
DOIs	https://doi.org/10.1021/acs.joc.1c01411
Publication status	Published - 1 Oct 2021

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/acs.joc.1c01411

Cite this

@article{333b684b83cd49079cf40f668f2b791e,

title = "Ortho-Deuteration of Aromatic Aldehydes via a Transient Directing Group-Enabled Pd-Catalyzed Hydrogen Isotope Exchange",

abstract = "A practical and scalable ortho-selective deuteration of aromatic aldehydes was accomplished by Pd-catalyzed hydrogen isotope exchange with deuterium oxide as an inexpensive deuterium source. The use of tert-leucine as a transient directing group facilitates the exchange, affording a wide range of ortho-deuterated aromatic aldehydes with deuterium incorporation up to 97%. The control experiments suggest that the addition of silver trifluoroacetate resists the unexpected reduction of Pd(II), while the theoretical study indicates a rapid reversible concerted metalation-deprotonation process.",

author = "Junhua Kong and Jiang, {Zhi Jiang} and Jiayuan Xu and Yan Li and Hong Cao and Yanan Ding and Bencan Tang and Jia Chen and Zhanghua Gao",

note = "Publisher Copyright: {\textcopyright} ",

year = "2021",

month = oct,

day = "1",

doi = "10.1021/acs.joc.1c01411",

language = "English",

volume = "86",

pages = "13350--13359",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Ortho-Deuteration of Aromatic Aldehydes via a Transient Directing Group-Enabled Pd-Catalyzed Hydrogen Isotope Exchange

AU - Kong, Junhua

AU - Jiang, Zhi Jiang

AU - Xu, Jiayuan

AU - Li, Yan

AU - Cao, Hong

AU - Ding, Yanan

AU - Tang, Bencan

AU - Chen, Jia

AU - Gao, Zhanghua

PY - 2021/10/1

Y1 - 2021/10/1

N2 - A practical and scalable ortho-selective deuteration of aromatic aldehydes was accomplished by Pd-catalyzed hydrogen isotope exchange with deuterium oxide as an inexpensive deuterium source. The use of tert-leucine as a transient directing group facilitates the exchange, affording a wide range of ortho-deuterated aromatic aldehydes with deuterium incorporation up to 97%. The control experiments suggest that the addition of silver trifluoroacetate resists the unexpected reduction of Pd(II), while the theoretical study indicates a rapid reversible concerted metalation-deprotonation process.

AB - A practical and scalable ortho-selective deuteration of aromatic aldehydes was accomplished by Pd-catalyzed hydrogen isotope exchange with deuterium oxide as an inexpensive deuterium source. The use of tert-leucine as a transient directing group facilitates the exchange, affording a wide range of ortho-deuterated aromatic aldehydes with deuterium incorporation up to 97%. The control experiments suggest that the addition of silver trifluoroacetate resists the unexpected reduction of Pd(II), while the theoretical study indicates a rapid reversible concerted metalation-deprotonation process.

UR - http://www.scopus.com/inward/record.url?scp=85115968712&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.1c01411

DO - 10.1021/acs.joc.1c01411

M3 - Article

AN - SCOPUS:85115968712

SN - 0022-3263

VL - 86

SP - 13350

EP - 13359

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 19

ER -

Ortho-Deuteration of Aromatic Aldehydes via a Transient Directing Group-Enabled Pd-Catalyzed Hydrogen Isotope Exchange

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this