Stereocontrolled synthesis of diamines from iodolactams

Knapp, Spencer; Levorse, Anthony T.

doi:10.1016/s0040-4039(00)95474-1

Cited by 19 publications

(3 citation statements)

References 19 publications

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“…1,3,5-Tri-N-substituted hexahydro-1,3,5-triazines have been focus of attention for the chemists and biologist for long time due to wide variety of biological activities associated with them such as antibacterial [1], antimicrobial [2], antitumor [3], muscle relaxant properties [4] and are reactive as azodyes [5]. They have also been used for protection of amino group [6,7] as well as for the synthesis of poly amines [8] and most of references are patent showing anti-HIV [9], herbicidal [10], and fungicidal [11] activity.…”

Section: Introductionmentioning

confidence: 99%

Green chemical synthesis of fluorinated 1,3,5-triaryl-s-triazines in aqueous medium under microwaves as potential antifungal agents

Dandia

Arya

Sati

et al. 2004

Journal of Fluorine Chemistry

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Section: Introductionmentioning

confidence: 99%

Green chemical synthesis of fluorinated 1,3,5-triaryl-s-triazines in aqueous medium under microwaves as potential antifungal agents

Dandia

Arya

Sati

et al. 2004

Journal of Fluorine Chemistry

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“…6 Knapp and Levorse utilized iodolactams, prepared from cyclization of N,O-bis(trimethylsilyl)amide derivatives, as intermediates for the preparation of cis-diamines. 7 We required (1R,3R,4S)-3,4-diaminocyclopentanol (1) and its stereoisomer 2 as scaffoldings for the construction of geometrically defined metal complexes. Despite the simplicity (molecular formula C 5 H 12 N 2 O) of this compound, neither it nor its diastereomers has been described in the literature.…”

mentioning

confidence: 99%

Stereocontrolled Synthesis of (1R,3R,4S)- and (1S,3R,4S)-3,4-diaminocyclopentanols

Guan

Green

Bergstrom

1999

Synlett

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Cis-syn and cis-anti-3,4-diaminocyclopentanols have been synthesized from cyclopentadiene in eight steps. The key transformations involved construction of benzyl ether protected cisdiazidocyclopentanols, and sequential reduction and hydrogenolysis to the unprotected diaminocyclopentanols.Despite the development of numerous methods to construct vicinal cyclic diamines and their widespread applications, 1-2 the stereospecific synthesis of cis-1,2-cyclopentanediamines is surprisingly uncommon. Among a few examples are the stereoselective trans addition of either N,N-dichlorourethane or N,N-dichloro-t-butylcarbamate to cyclic alkenes, followed by nucleophilic displacement of chloride with azide, and then reduction and hydrolysis to give cis-1,2-diamines. 3 Fraenkel et al. has described the synthesis of cis-cyclopentanediamines by two methods, 4-5 however both methods were limited to the synthesis of cyclopentanediamines containing other alkyl substituents on the amino groups. Bruncko, Khuong, and Sharpless reported the synthesis of cis-1,2-diamino-3-cyclopentene via diimidoselenium-mediated allylic amination. 6 Knapp and Levorse utilized iodolactams, prepared from cyclization of N,O-bis(trimethylsilyl)amide derivatives, as intermediates for the preparation of cis-diamines. 7 We required (1R,3R,4S)-3,4-diaminocyclopentanol (1) and its stereoisomer 2 as scaffoldings for the construction of geometrically defined metal complexes. Despite the simplicity (molecular formula C 5 H 12 N 2 O) of this compound, neither it nor its diastereomers has been described in the literature.In order to achieve the most direct high yield synthesis of these diamines, it was necessary to devise a new route that would provide control of the stereochemistry of the hydroxyl substituent as well as the two amino groups. The synthetic route that we developed is both high yield and efficient.Crandall et al., 8 have described a synthesis of 3-cyclopentanol from cyclopentadiene. Conversion of the latter to its benzyl ether and epoxidation according to Eaton's paper afforded a 1:1 mixture of cis and trans-3,4-epoxycyclopentanol benzyl ether in 94 % yield. 9 They were separated by silica gel column chromatography with hexanes and ethyl acetate. The trans isomer 3 was refluxed with sodium azide and ammonium chloride to give the azido alcohol 4 and its enantiomer. Mesylation of the alcohol 4 generated the azido mesylate, which was then refluxed with sodium azide and pyridine in DMF to afford cis-syn-3,4-diazidocyclopentanol benzyl ether 5. The overall yield of these three steps was 75%. Thin layer chromato-graphy indicated that it was one spot, while the 1 H and 13 C NMR proved it was functionalized exclusively on one face of the cyclopentane ring (Scheme). FigureReduction of vicinal diazides proved to be difficult. 10 Staudinger reduction, palladium-on-carbon, and platinum oxide at low hydrogen pressure did not lead to the corresponding vicinal diamines. However, the diamines were obtained when diazide 5 was hydrogenated at 800 psi in the presence of pl...

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“…For Scheme I to be operative requires that hydroxylamine 1 react faster with adduct 3 than with m-TFBSP. This is highly unlikely since the peroxide is much more electrophilic than 3.8 The remaining possibilities, Schemes II and III, are similar in that both involve ionization of 3 to an alkoxy nitrenium ion, k2, but they are different in that Scheme II utilizes trapping of the nitrenium ion (k3) by 3 to give the N-N bond, while Scheme III has trapping of ( 8) For example, amines typically react conveniently with 0-(mesi-tylenesulfonyOhydroxylamine at 0 °C,9 whereas they react readily with 2 at -78 °C.6 (9) Tamura, Y.; Minamikawa, J.; Ikeda, M. Synthesis 1977, 1.…”

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confidence: 99%

Oxidation of O-alkylhydroxylamines with bis[[(m-(trifluoromethyl)phenyl]sulfonyl] peroxide

Hoffman¹,

Christophe²

1988

J. Org. Chem.

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Stereocontrolled synthesis of diamines from iodolactams

Cited by 19 publications

References 19 publications

Green chemical synthesis of fluorinated 1,3,5-triaryl-s-triazines in aqueous medium under microwaves as potential antifungal agents

Green chemical synthesis of fluorinated 1,3,5-triaryl-s-triazines in aqueous medium under microwaves as potential antifungal agents

Stereocontrolled Synthesis of (1R,3R,4S)- and (1S,3R,4S)-3,4-diaminocyclopentanols

Oxidation of O-alkylhydroxylamines with bis[[(m-(trifluoromethyl)phenyl]sulfonyl] peroxide

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