ChemInform Abstract: AZIRIDINES. PART II. SYNTHESIS OF 1‐ALKYL‐2,3‐DIPHENYLAZIRIDINES BY GABRIEL′S S METHOD

Bartnik, R.; Mlostoń, Grzegorz; Leśniak, Stanisław

doi:10.1002/chin.197935207

Cited by 7 publications

(11 citation statements)

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“…Thiobenzophenone (2a) [28], 2,2,4,4-tetramethyl-3-thioxocyclobutanone (2b) [29], and adamantanethione (2c) [30] were obtained according to published procedures. trans-1-Methyl-2,3-diphenylaziridine (trans-1a) was prepared from erythro-2-(methylamino)-1,2-diphenylethanol by treatment with Ph 3 P/CCl 4 /Et 3 N, according to a known procedure [19], as well as cis-1a [31] and cis-1,2,3-triphenylaziridine (cis-1b) [32]. Dimethyl dicyanofumarate (DCFM; 7a) was synthesized from methyl cyanoacetate and SOCl 2 [16].…”

Section: Methodsmentioning

confidence: 99%

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

Mlostoń

Urbaniak

Domagała³

et al. 2009

Helvetica Chimica Acta

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The thermal reaction of trans-1-methyl-2,3-diphenylaziridine (trans-1a) with aromatic and cycloaliphatic thioketones 2 in boiling toluene yielded the corresponding cis-2,4-diphenyl-1,3-thiazolidines cis-4 via conrotatory ring opening of trans-1a and a concerted [2 þ 3]-cycloaddition of the intermediate (E,E)-configured azomethine ylide 3a (Scheme 1). The analogous reaction of cis-1a with dimethyl acetylenedicarboxylate (5) gave dimethyl trans-2,5-dihydro-1-methyl-2,5-diphenylpyrrole-3,4-dicarboxylate (trans-6) in accord with orbital-symmetry-controlled reactions (Scheme 2). On the other hand, the reactions of cis-1a and trans-1a with dimethyl dicyanofumarate (7a), as well as that of cis-1a and dimethyl dicyanomaleate (7b), led to mixtures of the same two stereoisomeric dimethyl 3,4-dicyano-1-methyl-2,5-diphenylpyrrolidine-3,4-dicarboxylates 8a and 8b (Scheme 3). This result has to be explained via a stepwise reaction mechanism, in which the intermediate zwitterions 11a and 11b equilibrate (Scheme 6). In contrast, cis-1,2,3-triphenylaziridine (cis-1b) and 7a gave only one stereoisomeric pyrrolidine-3,4-dicarboxylate 10, with the configuration expected on the basis of orbital-symmetry control, i.e., via concerted reaction steps (Scheme 10). The configuration of 8a and 10, as well as that of a derivative of 8b, were established by X-ray crystallography.

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Section: Methodsmentioning

confidence: 99%

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

Mlostoń

Urbaniak

Domagała³

et al. 2009

Helvetica Chimica Acta

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“…1:1, which in the 1 H-NMR spectrum showed, in addition 2 ) Thionyl chloride (SOCl 2 ) was used as the chlorinating agent and Et 3 N as the base. The starting material was consumed, but only a complex a mixture of products was obtained [8].…”

Section: Methodsmentioning

confidence: 99%

“…For this reason, trifluoromethylsubstituted -amino alcohols were explored as convenient substrates for the preparation of aziridines with a new substitution pattern. First attempts were made following Gabriel's method, which is based on the initial conversion of a -amino alcohol to the corresponding -halo amine and subsequent treatment with a base [8]. In the case of 4b (Ar = Ph, R =t-Bu), the attempted synthesis of the aziridine was unsuccessful 2 ).…”

Section: Fig 1 Ortep-plotmentioning

confidence: 99%

Synthesis of Three‐, Five‐, and Six‐Membered Heterocycles Derived from New β‐Amino‐α‐(trifluoromethyl) Alcohols

Obijalska

Mlostoń

Linden

et al. 2010

Helvetica Chimica Acta

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Nucleophilic trifluoromethylation of α-iminoketones 2, derived from arylglyoxal, with Ruppert-Prakash reagent (CF3SiMe3) offers a convenient access to the corresponding O-silylated β-imino-α-trifluoromethyl alcohols. In a 'one-pot' procedure, by treatment with NaBH4, these products smoothly undergo reduction and desilylation yielding the expected β-amino-α-trifluoromethyl alcohols 4. The latter were used as convenient starting materials for the synthesis of diverse trifluoromethylated heterocycles, including aziridines 5, 1,3-oxazolidines 8, 1,3-oxazolidin-2-ones 9, 1,3,2-oxazaphospholidine 2-oxides 10, 1,2,3-oxathiazolidine 2-oxides 11, and morpholine-2,3-diones 12. An optically active 5-trifluoromethyl-substituted 1,3-oxazolidin-2-one 9g was also obtained. Nucleophilic trifluoromethylation of -iminoketones 2, derived from arylglyoxal, withRuppert-Prakash reagent (CF 3 SiMe 3 ) offers a convenient access to the corresponding Osilylated -imino--trifluoromethyl alcohols. In a 'one-pot' procedure, by treatment with NaBH 4 , these products smoothly undergo reduction and desilylation yielding the expected β-amino--trifluoromethyl alcohols 4. The latter were used as convenient starting materials for the synthesis of diverse trifluoromethylated heterocycles, including aziridines 5, 1,3-oxazolidines 8, 1,3-oxazolidin-2-ones 9, 1,3,2-oxazaphospholidine 2-oxides 10, 1,2,3-oxathiazolidine 2-oxides 11, and morpholine-2,3-diones 12. An optically active 5-trifluoromethyl-substituted 1,3-oxazolidin-2-one 9g was also obtained.

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“…[6][7][8][9][10][11][12] The thermal fragmentation of b-lactams occurs by two different pathways, the rst one gives the starting ketene and imine (B) and the second pathway (A) gives alkene and isocyanate which could be trapped with amine to give the corresponding urea derivatives, Fischer found that the thermal fragmentation favours pathway A, while photolysis favours pathway B (Scheme 1).…”

Section: -35mentioning

confidence: 99%

Pyrolysis of azetidinone derivatives: a versatile route towards electron-rich alkenes, C-1 allylation and/or homologation of aldehydes

et al. 2014

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Pyrolysis of b-lactams and b-thiolactams led essentially to stereoselective synthesis of the high energy electron-rich Z-alkenes. Extension of this methodology to the pyrolysis of 3-allyloxy derivatives gave a simple direct route to the synthetically important 4-pentenal. These pyrolytic transformations convert aldehydes to aryloxyalkenes (a protected homologation) and 4-pentenal (a C-1 allylation and homologation). The starting 3-aryloxy and 3-allyloxy-b-lactams were synthesized by the standard

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ChemInform Abstract: AZIRIDINES. PART II. SYNTHESIS OF 1‐ALKYL‐2,3‐DIPHENYLAZIRIDINES BY GABRIEL′S S METHOD

Abstract: Die Chlorierung der erythro‐ und threo‐Formen der Alkohole (I) liefert die Chloride (II) ausschließlich in der threo‐Fonn.

Cited by 7 publications

References 0 publications

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

Synthesis of Three‐, Five‐, and Six‐Membered Heterocycles Derived from New β‐Amino‐α‐(trifluoromethyl) Alcohols

Pyrolysis of azetidinone derivatives: a versatile route towards electron-rich alkenes, C-1 allylation and/or homologation of aldehydes

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