Reactivity of Imines Towards 3‐Trifloxypropeniminium and Propyniminium Triflates

Rahm, Rainer; Maas, Gerhard

doi:10.1002/cber.19941270719

Cited by 12 publications

(10 citation statements)

References 22 publications

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“…(A formula scheme of a possible polymerization pathway is shown in the Supporting Information.) We have reported earlier that acetylenic iminium salts with an internal triple bond undergo a controlled Michael addition with N ‐phenylbenzaldimine and isoquinoline. [14a] The stronger polarization and better accessibility of the terminal alkynes 5 could be factors causing the reaction not to terminate after the first conjugate addition step.…”

Section: Resultsmentioning

confidence: 99%

Terminal Acetylenic Iminium Salts – Synthesis and Reactivity

et al. 2018

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Various types of terminal acetylenic iminium triflates (propyne iminium salts) featuring a ketiminium or an aldiminium group have been prepared for the first time by protiodesilylation of the corresponding trimethylsilyl‐substituted acetylenic iminium salts using triflic acid and catalytic silver(I) triflate. The high reactivity of the terminal C,C‐triple bond is documented herein by the facile Michael addition of nucleophiles and the exceptionally high dienophilic reactivity in Diels‐Alder reactions.

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Section: Resultsmentioning

confidence: 99%

Terminal Acetylenic Iminium Salts – Synthesis and Reactivity

et al. 2018

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“…Brought to you by | Purdue University Libraries Authenticated Download Date | 5/30/15 5:54 AM A number of chemical reactions have been performed with propyne iminium salts 1 [4,5,8,[21][22][23][24][25][26][27][28][29][30][31][32][33][34]. In contrast, only few reactions of propiolamidinium salts 3 are known.…”

Section: Introductionmentioning

confidence: 98%

Orthoamides and iminium salts, LXXXIX. Reactions of N,N,N′,N′,N″,N″,N′″,N′″-octamethyl-acetylene-bis(carboxamidinium) tetrafluoroborate with nucleophilic reagents – new methods for the preparation of amidinium salts and ketene aminalsa

Drandarov

Tiritiris

Kantlehner³

2015

Zeitschrift Für Naturforschung B

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The acetylene-bis(carboxamidinium) salt 4 dehydrates carboxylic acids to the corresponding anhydrides, as the byproduct 2-oxo-but-2-en-amidinium salt 6b was isolated. Aromatic hydroxy compounds and 2-furyl-methylmercaptan add to the triple bond of the salt 4 to give 2-aryloxy-and 2-alkylmercapto-but-2-enebis(amidinium) salts 7-9. According to this reaction principle, 2-organoamino-buten-2-ene-bis(amidinium) salts 10 and 11 were prepared from 4 and primary and secondary amines, whereas 4-chlorobenzhydrazide reacted with 4 to give the imidazole-3-carboxamidinium salt 13. The reaction of CH 2 -acidic compounds as malononitrile or ethyl cyanoacetate with the bis(amidinium) salt 4 affords 2-cyanomethylene-but-3-enamidinium salts 15. With the CH-acidic diethyl 2-bromomalonate, compound 4 undergoes a Michael-initiated ring closure cyclopropenation reaction with further ring opening by the released Br -to the corresponding 2-diethoxycarbonylmethylene-3-bromo-but-3-enamidinium salt 18. Unlike cyclopentadiene and furane, the reaction of N-methylpyrrole and bis(amidinium) salt 4 does not lead to Diels-Alder [4 + 2] cycloadduct but to the Michaeltype 1:1 adduct 20. Pyrrole-and thiophene-2-carboxamidinium salts 23-25 can be prepared from compound 4 and esters of glycine, N-methylglycine (sarcosine), and mercaptoacetic acid, respectively. The derivatives of quinoxaline-2-carboxamidinium salts 29 are accessible from aromatic 1,2-diamines and compound 4. The reaction of the CH 2 /NH-acidic cyanoacetamide with the bis(amidinium) salt 4 produced the 3-pyrroline-2-on derivatives 33.

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“…Their reactivity towards imines has also been reported. 18,19 Recently, we reported on a simple onepot metal-free synthesis of 2,4,5-trisubstituted pyridine derivatives and their N-oxides by [2þ2] cycloaddition of propyne iminium salts as electron-poor acetylenes to enaminones as an extension of the research recently developed in our laboratory. 20 We also recently reported on a simple, metal-free synthesis of polysubstituted benzene derivatives, where N,N-dimethylacetamide dimethyl acetal (DMADMA) served as the reagent and building block for generating aromatic final products.…”

Section: Introductionmentioning

confidence: 99%