PMID- 35613457
OWN - NLM
STAT- MEDLINE
DCOM- 20220609
LR  - 20230610
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Print)
IS  - 0002-7863 (Linking)
VI  - 144
IP  - 22
DP  - 2022 Jun 8
TI  - Site-Specific and Degree-Controlled Alkyl Deuteration via Cu-Catalyzed 
      Redox-Neutral Deacylation.
PG  - 9570-9575
LID - 10.1021/jacs.2c04382 [doi]
AB  - Deuterated organic compounds have become increasingly important in many areas; 
      however, it remains challenging to install deuterium site-selectively to 
      unactivated aliphatic positions with control of the degree of deuteration. Here, 
      we report a Cu-catalyzed degree-controlled deacylative deuteration of diverse 
      alkyl groups with the methylketone (acetyl) moiety as a traceless activating 
      group. The use of N-methylpicolino-hydrazonamide (MPHA) promotes efficient 
      aromatization-driven C-C cleavage. Mono-, di-, and trideuteration at specific 
      sites can be selectively achieved. The reaction is redox-neutral with broad 
      functional group tolerance. The utility of this method has been demonstrated in 
      forming a complete set of deuterated ethyl groups, merging with the Diels-Alder 
      reaction, a net devinylative deuteration, and the synthesis of the d(2)-analogue 
      of Austedo.
FAU - Zhou, Xukai
AU  - Zhou X
AD  - Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United 
      States.
FAU - Yu, Tingting
AU  - Yu T
AD  - Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United 
      States.
FAU - Dong, Guangbin
AU  - Dong G
AUID- ORCID: 0000-0003-1331-6015
AD  - Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United 
      States.
LA  - eng
GR  - R01 GM109054/GM/NIGMS NIH HHS/United States
PT  - Journal Article
PT  - Research Support, N.I.H., Extramural
DEP - 20220525
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 0 (Organic Chemicals)
RN  - AR09D82C7G (Deuterium)
SB  - IM
MH  - Catalysis
MH  - Deuterium
MH  - *Organic Chemicals
MH  - Oxidation-Reduction
PMC - PMC9486252
MID - NIHMS1835005
COIS- The authors declare no competing financial interests.
EDAT- 2022/05/26 06:00
MHDA- 2022/06/10 06:00
PMCR- 2023/06/08
CRDT- 2022/05/25 16:33
PHST- 2022/05/26 06:00 [pubmed]
PHST- 2022/06/10 06:00 [medline]
PHST- 2022/05/25 16:33 [entrez]
PHST- 2023/06/08 00:00 [pmc-release]
AID - 10.1021/jacs.2c04382 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2022 Jun 8;144(22):9570-9575. doi: 10.1021/jacs.2c04382. Epub 2022 
      May 25.