Utility of Hydrazidoyl Halides in Heterocycles: A New Route for the Synthesis of Alkylmercaptoheterocyclic Compounds

Elghandour, Ahmed H.; Ibrahim, M. K. A.; El‐Badry, B.; Waly, H. K.

doi:10.1080/10426509408036915

Cited by 8 publications

(1 citation statement)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, a few examples of the scaffold are known along with related thioimidates possessing α-oxidation including α-keto ( 8 ), α-oximino ( 9 ), and α-hydrazono ( 10 ) congeners (Figure ). − Despite the lack of straightforward, general methods to access them from simple building blocks, α-oxidized thioimidates exhibit a broad range of utility and interest including their use as metal-binding ligands, , as dyes, as intermediates in the synthesis of rare heterocycles, − pharmaceuticals, pesticides and fungicides, ,− and their occurrence as components of Maillard flavors in cooked food . It seems likely that the development of a general route to this class of rare molecules might serve to enhance their utility in a variety of applications.…”

Section: Introductionmentioning

confidence: 99%

Cycloaddition/Electrocyclic Ring Opening Sequence between Alkynyl Sulfides and Azodicarboxylates To Provide N,N-Dicarbamoyl 2-Iminothioimidates

Narangoda¹,

Kakeshpour

Lex³

et al. 2019

J. Org. Chem.

View full text Add to dashboard Cite

The α-oxidized thioimidates are useful bidentate ligands and are important motifs in pharmaceuticals, pesticides, and fungicides. Despite their broad utility, a direct route for their synthesis has been elusive. Herein, we describe a one-step synthesis of N,Ndicarbamoyl 2-iminothioimidates from easily accessible thioacetylenes and commercially available azodicarboxylates (20 examples, ≤99% yield). Additionally, the mechanism of the transformation was extensively explored by variable-temperature NMR, in situ IR, and quantum mechanical simulations. These experiments suggest that the reaction commences with a highly asynchronous [2 + 2] cycloaddition, which leads to a four-membered diazacyclobutene intermediate with a barrier consistent with the observed reaction rate. This intermediate was then isolated for subsequent kinetic measurements, which yielded an experimental barrier within 1 kcal/mol of the calculated barrier for a subsequent 4π electrocyclic ring opening leading to the observed iminothioimidate products. This method represents the first direct route to α-oxidized thioimidates from readily accessible starting materials.

show abstract

Section: Introductionmentioning

confidence: 99%

Cycloaddition/Electrocyclic Ring Opening Sequence between Alkynyl Sulfides and Azodicarboxylates To Provide N,N-Dicarbamoyl 2-Iminothioimidates

Narangoda¹,

Kakeshpour

Lex³

et al. 2019

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Extrusion Reactions Affording Aromatic Systems, Dienes and Polyenes

Guziec

2022

Organic Reactions

View full text Add to dashboard Cite

Extrusion reactions may be defined as chemical reactions in which an atom or small molecular fragment Y connected to two other atoms W and Z is lost from a molecule, leading to a product in which W becomes directly bonded to Z. Cheletropic reactions that afford aromatic or conjugated π systems by loss of a stable atomic or molecular fragment have also been classified as extrusion reactions. Typically, the fragments liberated in these reactions are small, stable inorganic molecules or atoms such as carbon monoxide, carbon dioxide, sulfur, sulfur monoxide, sulfur dioxide, selenium, tellurium, oxygen and nitrogen. This chapter primarily deals with the synthesis of arenes, heterocycles, 1,3‐dienes and polyenes using such extrusion processes. The utility of these reactions in the synthesis of sterically hindered molecules, dendrimers, pheromones, and other natural products are highlighted. The use of extrusion reactions for the “Click and Release” approach in drug development is also introduced.

show abstract

References

2000

Chemistry of Heterocyclic Compounds: A Series of Monographs

View full text Add to dashboard Cite

Utility of Hydrazidoyl Halides in Heterocycles: A New Route for the Synthesis of Alkylmercaptoheterocyclic Compounds

Cited by 8 publications

References 9 publications

Cycloaddition/Electrocyclic Ring Opening Sequence between Alkynyl Sulfides and Azodicarboxylates To Provide N,N-Dicarbamoyl 2-Iminothioimidates

Cycloaddition/Electrocyclic Ring Opening Sequence between Alkynyl Sulfides and Azodicarboxylates To Provide N,N-Dicarbamoyl 2-Iminothioimidates

Extrusion Reactions Affording Aromatic Systems, Dienes and Polyenes

References

Contact Info

Product

Resources

About