Rhodium/Copper Cocatalyzed Highly trans-Selective 1,2-Diheteroarylation of Alkynes with Azoles via C-H Addition/Oxidative Cross-Coupling: A Combined Experimental and Theoretical Study

Article abstract of DOI:10.1021/jacs.7b07242

Transition metal-catalyzed addition of diaryl alkynes with arylating reagents for the synthesis of tetraarylethylenes generally encounters rigorous reaction conditions and relies on the use of prefunctionalized substrates such as organic halides or surrogates and organometallic reagents. In this work, we establish a highly trans-selective 1,2-diheteroarylation of alkynes with azoles via a rhodium/copper cocatalyzed C-H addition/oxidative coupling process. Moreover, the diheteroarylation developed herein could open a door for the synthesis of heteroarene-doped tetraarylethylenes, and the photoluminescence (PL) spectra in THF-water mixtures and solid powder verify that these tetra(hetero)arylethylenes are aggregation-induced emission (AIE) active, building a new AIE molecule library. With a combination of experimental and theoretical methods, the reaction mechanism for addition/oxidative cross-coupling of internal alkynes with azoles has been investigated. Theoretical calculations reveal that the metalation/deprotonation of azole could occur with either rhodium or copper species. When azolylrhodium is formed, an alkyne could insert into the Rh-C bond. Another azolyl group could then transfer to rhodium from azolylcopper compound. The subsequent intramolecular trans-nucleophilic addition generates the second C-C bond. Meanwhile, the putative pathway for the formation of the hydroheteroarylated byproduct has also been explained by theoretical calculations.

Full text of DOI:10.1021/jacs.7b07242

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Article
Rhodium/Copper Co-Catalyzed Highly trans-Selective 1,2-
Diheteroarylation of Alkynes with Azoles via C–H Addition/Oxidative
Cross-Coupling: A Combined Experimental and Theoretical Study
Guangying Tan, Lei Zhu, Xingrong Liao, Yu Lan, and Jingsong You
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b07242 • Publication Date (Web): 17 Oct 2017
Downloaded from http://pubs.acs.org on October 17, 2017
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Rhodium/Copper Co-Catalyzed Highly trans-Selective 1,2-
Diheteroarylation of Alkynes with Azoles via C–H Addi-
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Theoretical Study
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INTRODUCTION
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RESULTS AND DISCUSSION
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ASSOCIATED CONTENT
AUTHOR INFORMATION
Corresponding Author
CONCLUSIONS
*
*
Notes
ACKNOWLEDGMENT
REFERENCES
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