Formal Insertion of Imines (or Nitrogen Heteroarenes) and Arynes into the C–Cl Bond of Carbon Tetrachloride

Li, Shengjun; Wang, Yi; Xu, Jian; Xie, Dong; Tian, Shi‐Kai; Yu, Zhi‐Xiang

doi:10.1021/acs.orglett.8b01845

Cited by 33 publications

(19 citation statements)

References 71 publications

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“…Each of 33 , 34 , and 35 was produced in a very good yield, starting with 1b , 1c , and 1d , respectively. Finally, when carbon tetrachloride ( 4c ) was used as solvent instead of CHCl 3 , chlorination of the 1,3-zwitterion from quinoline led to the formation of 32 18…”

Section: Resultsmentioning

confidence: 99%

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

et al. 2019

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We report here various pathways by which six-membered N-heteroaromatic compounds react with benzynes that are generated by the HDDA reaction. The initially formed 1,3-zwitterionic species (a) can collapse intramolecularly to give novel 1 : 1 adducts of the heterocycle and benzyne; (b) can react with an externally added, electrophilic third-component to give functionalized heterocyclic products; or (c) can react with an external protic nucleophile to produce, following collapse of the ion pair resulting from protonation of the zwitterion, a variety of three-component assemblies. Mechanisms for formation of some of the 1 : 1 adducts are supported by DFT methods. The scope of the protic nucleophilic coupling was also expanded to a two-pot operation by using triflic acid as a protic "non-nucleophile", followed by the addition of a suitably reactive nucleophile.

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Section: Resultsmentioning

confidence: 99%

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

et al. 2019

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“…Simple alkyl chlorides, especially chloroform, usually used as nucleophile by deprotonation to participate in the functionalization of imines and aryne [32–35] . In 2006, Asao and co‐workers reported the catalysts‐free three‐component cyclization of ortho ‐alkynylbenzaldehydes with primary amines and CHCl 3 to obtain 1,2‐dihydroisoquinoline skeletons (Scheme 34).…”

Section: Polychloroalkylation Of Iminementioning

confidence: 99%

“…In 2018, Yu and Tian reported similar reaction for trichloromethylation of imine to afford polychlorinated aniline derivatives, although they employed CCl 4 as an nucleophiles instead of CHCl 3 (Scheme 38). [35] The difference is that this method forms a C−Cl bond instead of a C−H bond at the ortho position of the benzene alkyne.…”

Section: Polychloroalkylation Of Iminementioning

confidence: 99%

“…Recently, with the development of radical chemistry, simple alkyl chlorides (such as dichloromethane, chloroform etc.) have been used as effective precursors to introduce the polychlorinated groups through the coupling with alkanes, [4–7] addition of olefins [9–26] and cyclizations [27–36] . Among them, due to the high reactivity of polychlorinated radical intermediates, the radical‐mediated polychloroalkylation groups have been considered to be an indispensable tool for the synthesis of complex polychlorinated compounds.…”

Section: Introductionmentioning

confidence: 99%

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Recent Developments in the Polychloroalkylation by Use of Simple Alkyl Chlorides

Liang

Ouyang

et al. 2020

Adv Synth Catal

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Owing to their easy availability and cheapness, simple alkyl chlorides are good raw materials for introducing complex polychlorinated groups. Polychlorinated hydrocarbons units, such as di‐ or trichloromethyl groups, not only widely found in pesticide and bioactive molecule, but also can be as a precursor to converted into different functional groups such as −COOH, −CHO and −CO. The direct polychloroalkylation reaction by using simple alkyl chlrides has been considered to be an important tool for synthesizing complex polychlorinated compounds. This review summarizes recent developments, especially free radical strategies, in the polychloroalkylation of different substrates (such as 2‐acylpyridines, benzyl tertiary amines, alkenes, imine and 1,n‐enynes). We hope that this review provides a new perspective on this field and also provides a reference to develop environmentally friendly and sustainable methods.

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“…Das sich bildende Vinylanion wird durch das positiv polarisierte Halogen neutralisiert, und man erhält das aminoarylierte Produkt 29 . Ähnliche Verbindungen sind durch den Angriff von Iminen an Arine und die Chlorierung in 2‐Position durch Tetrachlorkohlenstoff zugänglich, wobei das entstandene CCl 3 ‐Anion das sp 2 ‐hybridisierte Kohlenstoffatom der Heterocarbonylverbindung angreift . Eine entsprechende Reaktion für D‐A‐Cyclopropane wurde von der Gruppe um Studer zur Synthese von 1,3‐aminohalogenierten Produkten 30 realisiert .…”

Section: Insertionenunclassified

Über bislang nicht beachtete Parallelen in der Reaktivität von Arinen und Donor‐Akzeptor‐Cyclopropanen

Werz

Biju

2019

Angewandte Chemie

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Arine und Donor‐Akzeptor‐substituierte (D‐A‐)Cyclopropane sind zwei Klassen gespannter Systeme mit einer Vielzahl an möglichen Anwendungen in der organischen Synthese. In den letzten beiden Jahrzehnten hat die Chemie dieser beiden Spezies eine Renaissance erlebt, vor allem wegen der milden und zuverlässigen Methoden zu ihrer Herstellung oder Aktivierung. In der Regel führen Arine als leicht polarisierbare Systeme zur 1,2‐Disubstitution, während D‐A‐Cyclopropane als polarisierte Systeme zur 1,3‐Disubstitution neigen und dabei auffällige Ähnlichkeiten aufweisen. Die Umsetzungen mit 1,2‐ und 1,3‐Dipolen führen zu cyclischen Strukturen. Die mit Arinen entstehenden viergliedrigen cyclischen Intermediate können weiterreagieren, während die analogen fünfgliedrigen Cyclen hervorgehend aus D‐A‐Cyclopropanen meist die finalen Endprodukte darstellen. Es gibt jedoch einige Fälle, in denen sich diese Zwischenprodukte überraschend unterschiedlich verhalten. Dieser Kurzaufsatz zielt darauf ab, die Parallelen in der Reaktivität von Arinen und D‐A‐Cyclopropanen aufzuzeigen und somit Licht auf die bisher vernachlässigten Ähnlichkeiten dieser beiden reaktiven Spezies zu werfen.

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Formal Insertion of Imines (or Nitrogen Heteroarenes) and Arynes into the C–Cl Bond of Carbon Tetrachloride

Cited by 33 publications

References 71 publications

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

Recent Developments in the Polychloroalkylation by Use of Simple Alkyl Chlorides

Über bislang nicht beachtete Parallelen in der Reaktivität von Arinen und Donor‐Akzeptor‐Cyclopropanen

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