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^*

^*Corresponding author for this work

Research output: Journal Publication › Article › peer-review

21 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

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10.1021/acs.joc.1c01411

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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",

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year = "2021",

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

language = "English",

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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 - https://www.scopus.com/pages/publications/85115968712

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

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