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Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations.
J Org Chem. 2012 Mar 16; 77(6):2837-49.JO

Abstract

A new, general method for the synthesis of spiro[4,5]trienones is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the (18)O-labeling experiments and DFT calculations.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Tang BX
Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research (Ministry of Education), Hunan Normal University, Changsha 410081, China.
Zhang YH
No affiliation info available
Song RJ
No affiliation info available
Tang DJ
No affiliation info available
Deng GB
No affiliation info available
Wang ZQ
No affiliation info available
Xie YX
No affiliation info available
Xia YZ
No affiliation info available
Li JH
No affiliation info available

MeSH

AlkynesCatalysisCyclizationMolecular StructurePalladiumQuantum TheorySpiro Compounds

Pub Type(s)

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

Language

eng

PubMed ID

22360308

Citation

Tang, Bo-Xiao, et al. "Intramolecular Ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes Leading to Spiro[4,5]trienones: Scope, Application, and Mechanistic Investigations." The Journal of Organic Chemistry, vol. 77, no. 6, 2012, pp. 2837-49.
Tang BX, Zhang YH, Song RJ, et al. Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations. J Org Chem. 2012;77(6):2837-49.
Tang, B. X., Zhang, Y. H., Song, R. J., Tang, D. J., Deng, G. B., Wang, Z. Q., Xie, Y. X., Xia, Y. Z., & Li, J. H. (2012). Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations. The Journal of Organic Chemistry, 77(6), 2837-49. https://doi.org/10.1021/jo300037n
Tang BX, et al. Intramolecular Ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes Leading to Spiro[4,5]trienones: Scope, Application, and Mechanistic Investigations. J Org Chem. 2012 Mar 16;77(6):2837-49. PubMed PMID: 22360308.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes leading to spiro[4,5]trienones: scope, application, and mechanistic investigations. AU - Tang,Bo-Xiao, AU - Zhang,Yue-Hua, AU - Song,Ren-Jie, AU - Tang,Dong-Jun, AU - Deng,Guo-Bo, AU - Wang,Zhi-Qiang, AU - Xie,Ye-Xiang, AU - Xia,Yuan-Zhi, AU - Li,Jin-Heng, Y1 - 2012/03/07/ PY - 2012/2/25/entrez PY - 2012/3/1/pubmed PY - 2012/8/9/medline SP - 2837 EP - 49 JF - The Journal of organic chemistry JO - J Org Chem VL - 77 IS - 6 N2 - A new, general method for the synthesis of spiro[4,5]trienones is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the (18)O-labeling experiments and DFT calculations. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/22360308/Intramolecular_ipso_halocyclization_of_4__p_unsubstituted_aryl__1_alkynes_leading_to_spiro[45]trienones:_scope_application_and_mechanistic_investigations_ L2 - https://doi.org/10.1021/jo300037n DB - PRIME DP - Unbound Medicine ER -