PMID- 37487009
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20230802
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 145
IP  - 30
DP  - 2023 Aug 2
TI  - Enhancing Substrate-Metal Catalyst Affinity via Hydrogen Bonding: 
      Pd(II)-Catalyzed beta-C(sp(3))-H Bromination of Free Carboxylic Acids.
PG  - 16297-16304
LID - 10.1021/jacs.3c04223 [doi]
AB  - The achievement of sufficient substrate-metal catalyst affinity is a fundamental 
      challenge for the development of synthetically useful C-H activation reactions of 
      weakly coordinating native substrates. While hydrogen bonding has been harnessed 
      to bias site selectivity in existing C(sp(2))-H activation reactions, the 
      potential for designing catalysts with hydrogen bond donors (HBDs) to enhance 
      catalyst-substrate affinity and, thereby, facilitate otherwise unreactive 
      C(sp(3))-H activation remains to be demonstrated. Herein, we report the discovery 
      of a ligand scaffold containing a remote amide motif that can form a favorable 
      meta-macrocyclic hydrogen bonding interaction with the aliphatic acid substrate. 
      The utility of this ligand scaffold is demonstrated through the development of an 
      unprecedented C(sp(3))-H bromination of alpha-tertiary and alpha-quaternary free 
      carboxylic acids, which proceeds in exceedingly high mono-selectivity. The 
      geometric relationship between the NHAc hydrogen bond donor and the coordinating 
      quinoline ligand is crucial for forming the meta-macrocyclophane-like hydrogen 
      bonding interaction, which provides a guideline for the future design of 
      catalysts employing secondary interactions.
FAU - Hu, Liang
AU  - Hu L
AUID- ORCID: 0000-0002-2960-9560
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Meng, Guangrong
AU  - Meng G
AUID- ORCID: 0000-0002-3023-0654
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Chen, Xiangyang
AU  - Chen X
AUID- ORCID: 0000-0002-6981-7022
AD  - Department of Chemistry and Biochemistry, University of California Los Angeles, 
      Los Angeles, California 90095, United States.
FAU - Yoon, Joseph S
AU  - Yoon JS
AD  - UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and 
      Biochemistry, University of California, San Diego, La Jolla, California 92093, 
      United States.
FAU - Shan, Jing-Ran
AU  - Shan JR
AD  - Department of Chemistry and Biochemistry, University of California Los Angeles, 
      Los Angeles, California 90095, United States.
FAU - Chekshin, Nikita
AU  - Chekshin N
AUID- ORCID: 0000-0002-9687-3310
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Strassfeld, Daniel A
AU  - Strassfeld DA
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Sheng, Tao
AU  - Sheng T
AUID- ORCID: 0000-0001-5339-9834
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Zhuang, Zhe
AU  - Zhuang Z
AUID- ORCID: 0000-0001-6679-0496
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
FAU - Jazzar, Rodolphe
AU  - Jazzar R
AUID- ORCID: 0000-0002-4156-7826
AD  - UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and 
      Biochemistry, University of California, San Diego, La Jolla, California 92093, 
      United States.
FAU - Bertrand, Guy
AU  - Bertrand G
AD  - UCSD-CNRS Joint Research Laboratory (IRL 3555), Department of Chemistry and 
      Biochemistry, University of California, San Diego, La Jolla, California 92093, 
      United States.
FAU - Houk, K N
AU  - Houk KN
AUID- ORCID: 0000-0002-8387-5261
AD  - Department of Chemistry and Biochemistry, University of California Los Angeles, 
      Los Angeles, California 90095, United States.
FAU - Yu, Jin-Quan
AU  - Yu JQ
AUID- ORCID: 0000-0003-3560-5774
AD  - Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines 
      Road, La Jolla, California 92037, United States.
LA  - eng
PT  - Journal Article
DEP - 20230724
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
SB  - IM
EDAT- 2023/07/24 19:09
MHDA- 2023/07/24 19:10
CRDT- 2023/07/24 14:13
PHST- 2023/07/24 19:10 [medline]
PHST- 2023/07/24 19:09 [pubmed]
PHST- 2023/07/24 14:13 [entrez]
AID - 10.1021/jacs.3c04223 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2023 Aug 2;145(30):16297-16304. doi: 10.1021/jacs.3c04223. Epub 
      2023 Jul 24.