PMID- 32058963
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20210110
IS  - 2589-0042 (Electronic)
IS  - 2589-0042 (Linking)
VI  - 23
IP  - 2
DP  - 2020 Feb 21
TI  - Toward Rational Understandings of alpha-C-H Functionalization: Energetic Studies of 
      Representative Tertiary Amines.
PG  - 100851
LID - S2589-0042(20)30034-1 [pii]
LID - 10.1016/j.isci.2020.100851 [doi]
LID - 100851
AB  - Functionalization of alpha-C-H bonds of tertiary amines to build various alpha-C-X bonds 
      has become a mainstream in synthetic chemistry nowadays. However, due to lack of 
      fundamental knowledge on alpha-C-H bond strength as an energetic guideline, rational 
      exploration of new synthetic methodologies remains a far-reaching anticipation. 
      Herein, we report a unique hydricity-based approach to establish the first 
      integrated energetic scale covering both the homolytic and heterolytic energies 
      of alpha-C-H bonds for 45 representative tertiary amines and their radical cations. 
      As showcased from the studies on tetrahydroisoquinolines (THIQs) by virtue of 
      their thermodynamic criteria, the feasibility and mechanisms of THIQ oxidation 
      were deduced, which, indeed, were found to correspond well with experimental 
      observations. This integrated scale provides a good example to relate bond 
      energetics with mechanisms and thermodynamic reactivity of amine alpha-C-H 
      functionalization and hence, may be referenced for analyzing similar 
      structure-property problems for various substrates.
CI  - Copyright (c) 2020 The Author(s). Published by Elsevier Inc. All rights reserved.
FAU - Luo, Wenzhi
AU  - Luo W
AD  - Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua 
      University, Beijing 100084, China.
FAU - Yang, Jin-Dong
AU  - Yang JD
AD  - Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua 
      University, Beijing 100084, China. Electronic address: 
      jdyang@mail.tsinghua.edu.cn.
FAU - Cheng, Jin-Pei
AU  - Cheng JP
AD  - Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua 
      University, Beijing 100084, China; State Key Laboratory of Elemento-organic 
      Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China. 
      Electronic address: jinpei_cheng@mail.tsinghua.edu.cn.
LA  - eng
PT  - Journal Article
DEP - 20200121
PL  - United States
TA  - iScience
JT  - iScience
JID - 101724038
PMC - PMC6997867
OTO - NOTNLM
OT  - Organic Chemistry
OT  - Organic Synthesis
OT  - Physical Organic Chemistry
COIS- Declaration of Interests The authors declare no competing interests.
EDAT- 2020/02/15 06:00
MHDA- 2020/02/15 06:01
PMCR- 2020/01/21
CRDT- 2020/02/15 06:00
PHST- 2019/10/07 00:00 [received]
PHST- 2019/12/31 00:00 [revised]
PHST- 2020/01/14 00:00 [accepted]
PHST- 2020/02/15 06:00 [pubmed]
PHST- 2020/02/15 06:01 [medline]
PHST- 2020/02/15 06:00 [entrez]
PHST- 2020/01/21 00:00 [pmc-release]
AID - S2589-0042(20)30034-1 [pii]
AID - 100851 [pii]
AID - 10.1016/j.isci.2020.100851 [doi]
PST - ppublish
SO  - iScience. 2020 Feb 21;23(2):100851. doi: 10.1016/j.isci.2020.100851. Epub 2020 
      Jan 21.