The role of pH in the synthesis of diaziridines

Кузнецов, В. В.; Махова, Нина Н.; Strelenko, Yu. À.; Khmel'nitskii, L. I.

doi:10.1007/bf00959732

Cited by 14 publications

(19 citation statements)

References 6 publications

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“…We have examined the proposed mechanism of the diaziridine ring formation to identify those factors that most likely influence the reaction. [32][33][34] We found that yields of monocyclic diaziridines 1 synthesized by mixing the three components in water depended on pH of the reaction medium.…”

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 93%

“…32,33 If so, the first step of the diaziridine synthesis is an interaction of the carbonyl compound with primary aliphatic amine (or ammonia) leading to α-aminocarbinol 22. The transformation of this then occurs via protonation with formation of oxonium ion 23 followed by its dehydration into carbeniumiminium cation 24, and should depend upon pH of the medium by analogy with the other α-aminomethylation reactions.…”

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

“…32,33 The dependence of the 1,3,3-trialkyldiaziridines 25 and 1,2,3-trialkyldiaziridines 26 yields upon the pH of the reaction medium is presented in Figs. 1 and 2 according to equations 2 and 3, respectively.…”

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

“…Path C is evidently most favorable for the synthesis of bicyclic products 29. The medium pH-dependent approach to diaziridine synthesis from amines, carbonyl compounds and aminating reagents in water (or the water-MeOH mixture) allowed to prepare a lot of diaziridines 1 with different kinds of substituents in both carbonyl compounds and amines, including reagents with electron-withdrawing substituents, [32][33][34] sterically hindered 1-aminoadamantane, 36 α-acethylenic aldehydes, 37 and to synthesize derivatives previously inaccessible, e.g. 30-32.…”

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

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Synthesis of monocyclic diaziridines and their fused derivatives

Махова¹,

Petukhova²,

Кузнецов³

2008

Arkivoc

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Diaziridines and their fused analogues have a wide-range potential as a test subjects for theoretical and practical application. This review covers our investigations focused on the development of optimal methods for the synthesis of monocyclic and fused diaziridine derivatives. Several approaches to the preparation of monocyclic diaziridine derivatives were developed: (1) a synthesis of 3,3-di-and 1,3,3-trialkylmono-and α,ω-bis(diaziridin-1-yl)alkanes from ketoxime O-sulfonates and ammonia, and primary aliphatic amines, respectively, as well as of practically previously inaccessible 3-monoalkyldiaziridines from ammonium salts of aldoxime O-sulfonic acids and ammonia (2) a synthesis of diaziridines from carbonyl compounds, primary aliphatic amines, and aminating reagents in water (or a water-MeOH mixture) at controlled pH of the medium, as well as from carbonyl compounds, amines and N-chloroalkylamines in aprotic solvents in the presence of K 2 CO 3, and (3) a synthesis of 1,2,3-trialkyldiaziridines from Nchloroalkylamines without carbonyl compounds in the presence of primary aliphatic amines at high pressure. As regards fused diaziridine derivatives, general and simple methods were developed to prepare four types of these structures: 1,5-diazabicyclo[3.1.0]hexanes, 1,6-diazabicyclo[4.1.0]heptanes, 1,3,5-triazabicyclo[3.1.0] hexanes, including the parent compound and 2,4-nonsubstituted structures, and 1,3,6-triazabicyclo[3.1.0]hexanes, the latter being previously unknown. The diastereomers have been isolated for 3,3′-bi-and 1,1′-alkylenebisdiaziridines. As a whole the investigations performed in our laboratory have resulted in the simple and general methods for preparing any kind of monocyclic and fused diaziridine derivatives that give high opportunities in the study of their chemical and stereochemical properties, and applications.

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Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 93%

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

Section: 3′-bidiaziridines From Diimines Of Glyoxal and 12-bis(metmentioning

confidence: 99%

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Synthesis of monocyclic diaziridines and their fused derivatives

Махова¹,

Petukhova²,

Кузнецов³

2008

Arkivoc

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“…In the first stage of the study, 1 (2 aminoethyl) 3,3 dimethyldiaziridine (4) described in our previous work, 7 which has already contained one 3,3 dimethyldiaziridine fragment, was used as the amine for the preparation of compound 1a. However, amines that did not react with the initial oxime esters 3, namely, Et 2 NH and Et 3 N, rather than an excess of amine 4 were used as the bases for binding arenesulfonic acids.…”

mentioning

confidence: 99%

Synthesis and structure of 1-[ω-(3,3-dialkyldiaziridin-1-yl)alkyl]-3,3-dialkyldiaziridines

2007

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Synthesis and structure of 1 [ω ω ω ω ω (3,3 dialkyldiaziridin 1 yl)alkyl] 3,3 dialkyldiaziridinesA method for the synthesis of 1 [ω (3,3 dialkyldiaziridin 1 yl)alkyl] 3,3 dialkyldiaziridines based on the reaction of ketoxime O arenesulfonates with alkylenediamines was developed. Diastrereomers (the racemic and meso forms) of 1 [2 (3,3 dimethyldiaziridin 1 yl)ethyl] 3,3 dimethyldiaziridine were isolated. The structure of the meso form was confirmed by X ray diffraction analysis.* Dedicated to Academician V. A. Tartakovsky on his 75th birthday. Scheme 1R 1 = R 2 = R 3 = Alk Scheme 2 α,ω Bis(3,3 dialkyldiaziridin 1 yl)alkanes Russ.

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Synthesis and Evaluation as Glycosidase Inhibitors of Carbasugar‐Derived Spirodiaziridines, Spirodiazirines, and Spiroaziridines

Kapferer

Birault

Poisson

et al. 2003

Helvetica Chimica Acta

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Dedicated to Professor Wolfgang Steglich on the occasion of his 70th birthdayThe spirodiaziridines 6 and 9, potential inhibitors of a-and b-glucosidases, were prepared from the validoxylamine A-derived cyclohexanone 5. The trimethylsilyl protecting groups of 5 are crucial for the formation of 6 in good yields. Oxidation of 6 gave 7. The diaziridine 6 (pK HA 2.6) and the diazirine 7 did not inhibit the b-glucosidases from almonds, the b-glucosidase from Caldocellum saccharolyticum, and the aglucosidase from yeast. The N-benzyl diaziridine 9 is a very weak inhibitor of the a-glucosidase, but did not inhibit the b-glucosidases. To see whether the weak inhibition is due to the low basicity of the diaziridines or to geometric factors, we prepared the spiro-aziridines 21 and 25 and 1-epivalidamine (32). The known cyclohexanone 10 was methylenated and epoxidised to 16 and 17. Azide opening of 16 and 17, mesylation, LiAlH 4 reduction, and deprotection gave the aziridines 21 and 25 respectively. 1-Epivalidamine (32) was prepared from the known carba-glucose 29. The aziridine 25 (pK HA 6.8) is a weak irreversible inhibitor of the b-glucosidase from Caldocellum saccharolyticum and a weak reversible inhibitor of the a-glucosidase from yeast, but did not inhibit the b-glucosidases from almonds. The poorly stable aziridine 21 weakly inhibited the three enzymes. Similarly, 1-epivalidamine (pK HA 8.4) proved only a weak inhibitor. The known cyclopentylamine 34 (pK HA 7.9), however, is a micromolar inhibitor of these enzymes. The much stronger inhibition by 34 is related to the pseudoaxial orientation of its amino group.Introduction. ± Alkoxydiaziridines of type 1 (Scheme 1) possess trans-oriented Natom lone-pairs located above and below the average plane of the pyranose ring and oriented more or less parallel to the ring plane. These diaziridines may, thus, inhibit both a-and b-glucosidases 3 ). The inhibition of b-glycosidases by diaziridines of this type may provide evidence for the correlation between the change of the pyranose-ring conformation, orienting the scissile bond in a pseudoaxial orientation, and the proton transfer to the glycosidic heteroatom characterising the reaction coordinate linking the ground and transition states of the rate-determining step. The diaziridines 1 may be accessible by deprotection of the known benzyl ethers 2 [2]. We were, however, concerned about the low basicity and the fragility of alkoxydiaziridines in aqueous solution. Exploratory experiments indeed showed that the diaziridines 1 are not sufficiently stable [3], so that we aimed at the synthesis of the carba analogues 6. To differentiate between the effects of shape and charge on the inhibition, we also required the related spiro-aziridines 21 and 25 4 ) (Scheme 2), and 1-epivalidamine

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The role of pH in the synthesis of diaziridines

Cited by 14 publications

References 6 publications

Synthesis of monocyclic diaziridines and their fused derivatives

Synthesis of monocyclic diaziridines and their fused derivatives

Synthesis and structure of 1-[ω-(3,3-dialkyldiaziridin-1-yl)alkyl]-3,3-dialkyldiaziridines

Synthesis and Evaluation as Glycosidase Inhibitors of Carbasugar‐Derived Spirodiaziridines, Spirodiazirines, and Spiroaziridines

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