Journal
ACS CATALYSIS
Volume 9, Issue 7, Pages 6372-6379Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b01273
Keywords
C-H activation; cross-coupling; heteroarylation; regioselectivity; iridium catalysis
Categories
Funding
- National NSF of China [21432005, 21502123]
- Comprehensive Training Platform of Specialized Laboratory, College of Chemistry, Sichuan University
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The development of a rational strategy to achieve the complete regioselectivity and the capability to switch regioselectivity is an appealing, yet challenging, puzzle in transition-metal-catalyzed oxidative Ar-H/Ar-H cross-coupling. Disclosed herein is an iridium-catalyzed C2/C4 regioselective C-H heteroarylation of indoles with the help of a pivaloyl group at the C3 position. The judicious choice of the catalytic systems allows the C2-heteroarylation of indole via a concerted metalation-deprotonation (CMD) process and the C4-heteroarylation via a trimolecular electrophilic substitution (S(E)3) pathway. The oxidants Cu(OAc)(2)H2O and Ag2O are demonstrated to play a vital role in the C2/C4 regioselectivity. In this Article, a heteroaryl-Ir(III)-heteroaryl complex prior to reductive elimination is successfully isolated and characterized, which represents the first example of capturing the bis(hetero)aryl metallic intermediate in oxidative Ar-H/Ar-H cross-coupling. The regiodivergent heteroarylation of indoles developed herein provides an opportunity to rapidly assemble diverse C4- and C2-heteroarylated indoles.
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