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Palladium-Catalyzed [2+2+1] Spiroannulation via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization.
Angew Chem Int Ed Engl. 2020 01 07; 59(2):653-657.AC

Abstract

Palladium-catalyzed alkene-directed cross-coupling of aryl iodide with another aryl halide through C-H arylation opens a unique avenue for unsymmetrical biaryl-derived molecules. However, homo-coupling of aryl iodides often erodes the overall synthetic efficiency. Reported herein is a highly chemoselective Pd0 -catalyzed alkyne-directed cross-coupling of aryl iodides with bromophenols, which was subsequently followed by phenol dearomatization to furnish a very attractive [2+2+1] spiroannulation. Notably, possible homo-coupling of aryl iodides was not observed at all. Mechanistic studies indicated that a five-membered aryl/vinyl palladacycle most likely accounts for promoting the key step of biaryl cross-coupling.

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Authors+Show Affiliations

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, China.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, China.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, China.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, China.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, China.

Pub Type(s)

Journal Article

Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

31654599

Citation

Zuo, Zhijun, et al. "Palladium-Catalyzed [2+2+1] Spiroannulation Via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization." Angewandte Chemie (International Ed. in English), vol. 59, no. 2, 2020, pp. 653-657.

Zuo Z, Wang J, Liu J, et al. Palladium-Catalyzed [2+2+1] Spiroannulation via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization. Angew Chem Int Ed Engl. 2020;59(2):653-657.

Zuo, Z., Wang, J., Liu, J., Wang, Y., & Luan, X. (2020). Palladium-Catalyzed [2+2+1] Spiroannulation via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization. Angewandte Chemie (International Ed. in English), 59(2), 653-657. https://doi.org/10.1002/anie.201909557

Zuo Z, et al. Palladium-Catalyzed [2+2+1] Spiroannulation Via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization. Angew Chem Int Ed Engl. 2020 01 7;59(2):653-657. PubMed PMID: 31654599.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Palladium-Catalyzed [2+2+1] Spiroannulation via Alkyne-Directed Remote C-H Arylation and Subsequent Arene Dearomatization. AU - Zuo,Zhijun, AU - Wang,Jing, AU - Liu,Jingjing, AU - Wang,Yaoyu, AU - Luan,Xinjun, Y1 - 2019/11/18/ PY - 2019/07/29/received PY - 2019/09/23/revised PY - 2019/10/28/pubmed PY - 2019/10/28/medline PY - 2019/10/27/entrez KW - C−H activation KW - aryl halides KW - cross-coupling KW - dearomatization KW - palladacycles SP - 653 EP - 657 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 59 IS - 2 N2 - Palladium-catalyzed alkene-directed cross-coupling of aryl iodide with another aryl halide through C-H arylation opens a unique avenue for unsymmetrical biaryl-derived molecules. However, homo-coupling of aryl iodides often erodes the overall synthetic efficiency. Reported herein is a highly chemoselective Pd0 -catalyzed alkyne-directed cross-coupling of aryl iodides with bromophenols, which was subsequently followed by phenol dearomatization to furnish a very attractive [2+2+1] spiroannulation. Notably, possible homo-coupling of aryl iodides was not observed at all. Mechanistic studies indicated that a five-membered aryl/vinyl palladacycle most likely accounts for promoting the key step of biaryl cross-coupling. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/31654599/Palladium_Catalyzed_[2+2+1]_Spiroannulation_via_Alkyne_Directed_Remote_C_H_Arylation_and_Subsequent_Arene_Dearomatization_ DB - PRIME DP - Unbound Medicine ER -