Synthesis of Carbocycles and Heterocycles via Tandem Reaction of Arynes

Arynes are highly reactive intermediate that have attracted considerable attention of chemists since their discovery over a century ago. In 1953, Roberts confirmed the formation of aryne through a 14C-labeling experiment of chlorobenzene. Arynes are not generally amenable to isolation and storage, accordingly, a diverse array of aryne generation methods, including dehy-drohalogenation of halobenzenes, elimination reactions of diaryliodonium salts, triaryloxonium ions, aryl sulfonium salts, fluoride-induced elimination of ortho-silylaryl triflates, the hexadehydro-Diels-Alder reaction of an al-kyne and a 1,3-diyne (HDDA) and so on, have been developed. Among these methods, 2-(trime- thylsilyl)aryl trifluoromethanesulfonates are useful reagents, which can generate arynes through fluoride-induced reaction under very mild conditions. Since the discovery of Kobayashi’s reagent, the past two decades have witnessed remarkable progress of arynes chemistry. As one of the most reactive organic species, arynes have been used widely in synthetic chemistry, medicinal chemistry and advanced functional materials. Owing to their distinct electronic properties, arynes can serve as dienophiles in a series of pericyclic reactions, insertion- cyclization, dearomatization, and multicomponent coupling reactions. In particular, the tandem reactions of arynes provide a powerful tool for the rapid construction of various carbocycles and heterocycles.

This book can be used as a reference for college teachers, graduate students, and researchers in the field of organic chemistry, fine chemistry and drug synthesis.

Sample Chapter(s)
Preface (20 KB)

Components of the Book:

Preface

Brief Introduction of the Authors

Chapter 1. Synthesis of functionalized carbocycles through tandem annulations of arynes

1. Direct assembly of polysubstituted naphthalenes via a tandem reaction of benzynes and α-cyano-β-methylenones
2. The synthesis of benzo[b]fluoranthenes and spiroacridines from fluorene-derived alkenes and N-arylimines via a tandem reaction with benzynes
3. Synthesis of sulfilimines via multicomponent reaction of arynes, sulfamides and thiosulfonates
4. Multicomponent reaction of phosphines, benzynes, and CO2: facile synthesis of stable zwitterionic phosphonium inner salts
5. Divergent synthesis of functionalized thioethers via multicomponent reaction of benzynes

Chapter 2. Synthesis of oxygen-containing heterocycles through tandem annulations of arynes

6. Highly efficient synthesis of 9-aminoxanthenes via the tandem reaction of arynes with salicyl N-tosylimines
7. Synthesis of 9-phenol-substituted xanthenes by cascade O-insertion/1,6-conjugate addition of benzyne with ortho- hydroxyphenyl substituted para-quinone methides
8. Construction of 9-functionalized xanthenes via Diels-Alder reaction of stable ortho-quinone methides and arynes
9. Facial synthesis of trifluoromethylated xanthenes via tandem reaction of arynes and 2-trifluoroacetylphenols

Chapter 3. Synthesis of nitrogen-containing heterocycles through tandem annulations of arynes

10. Diastereoselective synthesis of N‑aryl tetrahydroquinolines and N‑aryl indolines by the tandem reaction of arynes
11. Transition-metal-free synthesis of multisubstituted N-arylindoles via reaction of arynes and α-amino ketones
12. Reaction of aryne with aza-Morita-Baylis-Hillman adducts: Synthesis of 4-quinolones and N-arylation products
13. Transition-metal-free synthesis of 4-amino isoquinolin-1(2H)-ones via tandem reaction of arynes and oxazoles
14. Synthesis of hexahydrophenanthridines via the tandem reaction of benzynes
15. Aryne-induced dearomatized phosphonylation of electron-deficient azaarenes

Chapter 4. Synthesis of sulfur-containing heterocycles through tandem annulations of arynes

16. Construction of 6H-benzo[c]thiochromenes via a tandem reaction of arynes with thionoesters

Conclusions

Readership: Students, academics, teachers and other people attending or interested in the field of organic chemistry, fine chemistry and drug synthesis.

		Preface Lin He, Zhihua Cai, Pei Xie PDF (20 KB)

		Brief Introduction of the Authors Lin He, Zhihua Cai, Pei Xie PDF (74 KB)

		Chapter 1. Synthesis of functionalized carbocycles through tandem annulations of arynes Lin He, Zhihua Cai, Pei Xie PDF (1873 KB)

		Chapter 2. Synthesis of oxygen-containing heterocycles through tandem annulations of arynes Lin He, Zhihua Cai, Pei Xie PDF (737 KB)

		Chapter 3. Synthesis of nitrogen-containing heterocycles through tandem annulations of arynes Lin He, Zhihua Cai, Pei Xie PDF (1641 KB)

		Chapter 4. Synthesis of sulfur-containing heterocycles through tandem annulations of arynes Lin He, Zhihua Cai, Pei Xie PDF (349 KB)

		Conclusions Lin He, Zhihua Cai, Pei Xie PDF (19 KB)

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Lin He
He received his B.S. degree from Qufu Normal University in 2002 and his M.Sc. in organic chemistry from the University of Science and Technology of China in 2005. Three years later, he got his Ph.D. degree from Institute of Chemistry, Chinese Academy of Sciences (ICCAS). Then, he joined Shihezi University as a lecture. He was promoted to associate professor in 2009 and advanced to full professor in 2014.

Zhihua Cai
He received his B.S and M.S degree in 2009 and 2012 from Shihezi University under the guidance of Prof. Lin He. He received his PhD degree from Uni-versity of Chinese Academy of Sciences in 2019 under the guidance of Prof. Gang Li. Then, he joined Shihezi University, where he is now an associate professor. His research interests include organosilicon and aryne chemistry.

Pei Xie
She was born in Dazhou, P. R. of China in 1997. She received her B.S. and Ph.D. degree in 2018 and 2023 from Shihezi University under the guidance of Prof. Lin He. She is currently a Postdoc student in the research group of Professor ChengXi Li at Zhejiang University-Hangzhou Global Scientific and Tech-nological Innovation Center. Her research interests include aryne chemistry and chemical biology.

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