A facile one-pot synthesis of 2-(prop-2-yn-1-ylidene)-2,3-dihydro-1,4-thiazepines

Date

2020-11-01

Author

Yılmaz, Elif Serel
Zora, Metin

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

109
views

0
downloads

An unprecedented method for the synthesis of 2-(prop-2-yn-1-ylidene)-2,3-dihydro-1,4-thiazepines from N-(2,4-pentadiynyl) beta-enaminones is reported. Upon treatment with Lawesson's reagent, N-(2,4-pentadiynyl) beta-enaminones were thionated to furnish N-(2,4-pentadiynyl) beta-enaminothiones, which immediately underwent 7-exo-dig cyclization to generate 2-(prop-2-yn-1-ylidene)-2,3-dihydro-1,4-thiazepines in one-pot. A general trend was observed for various N-(2,4-pentadiynyl) beta-enaminones and cyclization proceeded with broad functional group tolerance. This operationally easy method may provide quick access to a library of functionalized 1,4-thiazepines in the field of pharmaceutical chemistry.

Subject Keywords

Organic Chemistry, alkynes, cyclization, β-enaminones, Lawesson’s reagent, N-propargylic N-(2,4-pentadiynyl) β-enaminothiones, 1,4-thiazepines

URI

https://hdl.handle.net/11511/69318

Journal

SYNTHETIC COMMUNICATIONS

DOI

https://doi.org/10.1080/00397911.2020.1850795

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

A new approach for the synthesis of spiro and gem-dimethyl-substituted 1,4-oxazepines from N-propargylic beta-enaminones Karadeniz, Eda; Kelgökmen, Yılmaz; Zora, Metin (Wiley, 2020-11-01) An efficient and general method for the synthesis of spiro-1,4-oxazepines and 3,3-dimethyl-1,4-oxazepines is reported. When treated with ZnI2 and AgSbF6 in refluxing DCE, cyclohexane-embedded N-propargylic beta-enaminones underwent 7-exo-dig cyclization to afford spiro-1,4-oxazepines, specifically 12-methylene-11-oxa-7-azaspiro[5.6]dodeca-7,9-dienes, in good to high yields. Accordingly, N-(1,1-dimethyl)propargylic beta-enaminones produced 3,3-dimethyl-1,4-oxazepines. Cyclization was found to be general for ...
A facile synthesis of 6-chloro-2-methylene-2,3-dihydro-1,4-oxazepines from N-propargylic beta-enaminones Ibis, Ozge; Zora, Metin (Elsevier BV, 2020-11-01) A new and efficient method for the synthesis of 6-chloro-substituted 2-methylene-2,3-dihydro-1,4-oxazepines has been demonstrated. Upon treatment with N-chlorosuccinimide in acetonitrile, N-propargylic beta-enaminones underwent chlorination to afford alpha-chlorinated N-propargylic beta-enaminones, which was then subjected to electrophilic cyclization with zinc chloride in refluxing chloroform to yield 6-chloro-2-methylene-2,3-dihydro-1,4-oxazepines. It was shown for the first time that on N-propargylic bet...
A New Strategy for the Synthesis of 4-Propargyl-Substituted 1H-Pyrroles from N-(5-phenyl-2,4-pentadiynyl) beta-Enaminones Yılmaz, Elif Serel; Zora, Metin (2019-10-09) A new method for the synthesis of 4-propargyl-substituted 1H-pyrroles is described. When treated with sodium hydride in refluxing dichloromethane, N-(5-phenyl-2,4-pentadiynyl) beta-enaminones, synthesized by the coupling of N-propargylic beta-enaminones with phenylacetylene, afforded 4-propargyl-substituted pyrrole derivatives. This conversion was general for a variety of N-(5-phenyl-2,4-pentadiynyl) beta-enaminones and displayed broad functional group tolerance. During the reaction, not only cyclization of...
A facile synthesis of (+/-)-mintlactone Tanyeli, Cihangir; Demir, AS (Informa UK Limited, 1997-01-01) (+/-)-Mintlactone has been synthesized by applying a novel effective synthetic sequence. 4-Methylcyclohexanone was subjected to acetoxylation with Pb(OAc)(4). Hydrolysis followed by reaction with 2-chloroprogionyl chloride,then treatment with triethyl phosphite and, finally, Horner-Emmons-type intramolecular cyclization afforded (+/-)-Mintlactone.
One-Pot Synthesis of Spiro-2H-pyrroles fromN-Propargylic beta-Enaminones KARADENİZ, EDA; Zora, Metin (Georg Thieme Verlag KG, 2019-06-01) A simple and general one-pot method for the synthesis of spiro-2 H -pyrroles has been developed. Initially, cyclohexane-embedded -enaminones with internal alkyne functionality were synthesized by conjugate addition of 1-ethynylcyclohexylamine to ,-alkynic ketones, followed by palladium-catalyzed coupling of the resulting N -propargylic -enaminones with aryl iodides. When subjected to basic conditions, the cyclohexane-embedded -enaminones with internal alkyne functionality underwent tandem nucleophilic cycli...

Citation Formats

E. S. Yılmaz and M. Zora, “A facile one-pot synthesis of 2-(prop-2-yn-1-ylidene)-2,3-dihydro-1,4-thiazepines,” SYNTHETIC COMMUNICATIONS, 2020, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/69318.