Towards Rational Understandings of α-C–H Functionalization: Energetic Studies of Representative Tertiary Amines

14 Pages Posted: 18 Nov 2019

See all articles by Wenzhi Luo

Wenzhi Luo

Tsinghua University - Department of Chemistry

Jin-Dong Yang

Tsinghua University - Department of Chemistry

Jin-Pei Cheng

Tsinghua University - Department of Chemistry

Date Written: November 12, 2019

Abstract

Functionalization of α-C–H bonds of tertiary amines to build various α-C–X bonds has become a mainstream in synthetic chemistry. However, due to lack of fundamental knowledge on α-C–H bond strength, 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 α-C–H bonds for 45 representative tertiary amines and their radical cations. As showcased from the studies on tetrahydroisoquinolines by virtue of the thermodynamic criteria, the feasibility and mechanisms of their oxidation were deduced, and indeed, were found to correspond well with experimental observations. This energetic scale actually provides a good example among the α-C–H categories to relate the bond thermodynamics with mechanisms/reactivity of their α-C–H transformation, and hence, may be referenced for analyzing similar structure-property problems for a wide variety of substrates.

Keywords: tertiary amine; C–H functionalization; thermodynamics; bond dissociation energy; mechanism; hydride transfer; electron transfer; hydrogen-atom transfer; cross-dehydrogenative coupling

Suggested Citation

Luo, Wenzhi and Yang, Jin-Dong and Cheng, Jin-Pei, Towards Rational Understandings of α-C–H Functionalization: Energetic Studies of Representative Tertiary Amines (November 12, 2019). Available at SSRN: https://ssrn.com/abstract=3485344 or http://dx.doi.org/10.2139/ssrn.3485344

Wenzhi Luo

Tsinghua University - Department of Chemistry

Beijing, 100084
China

Jin-Dong Yang (Contact Author)

Tsinghua University - Department of Chemistry ( email )

Beijing, 100084
China

Jin-Pei Cheng

Tsinghua University - Department of Chemistry ( email )

Beijing, 100084
China

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