Reduction of 1,3-diphenyl-2,2-dihaloaziridines with tri-n-butyltin hydride

Yamanaka, Hiroki; Kikui, Junichi; Teramura, Kazuhiro; Ando, Teiichi

doi:10.1021/jo00886a005

Cited by 30 publications

(12 citation statements)

References 7 publications

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“…16 Yamanaka has also demonstrated the formation of halogenated aziridines via aziridinyl radical intermediates. 17 Selective reduction of 2,2-dihalogenated aziridines with H-SnBu 3 through a radical chain reaction affords the dehalogenated aziridine via a carbon-centered radical species.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Selenoaziridines: A Study on Stereochemical Outcomes of the Reaction of Aziridine Radicals and Anions Generated from Iodoaziridines

Boultwood

Bull

2019

ACS Omega

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The synthesis of a new functional group in the form of selenyl-substituted aziridines is described. Selenoaziridines are stereoselectively prepared by functionalization of intact aziridine precursors involving radical and anionic intermediates. Radicals are generated from cis - N -Ts iodoaziridines by activation of the C–I bond using alkoxides as a source of single electrons. These form predominantly trans -substituted selenoaziridines dependent on the size of the diselenide. cis -Aziridinyllithiums generated by Li–I exchange also react with diselenides stereospecifically to form a range of cis -selenoaziridines. Proposals for the stereochemical outcome are presented.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Selenoaziridines: A Study on Stereochemical Outcomes of the Reaction of Aziridine Radicals and Anions Generated from Iodoaziridines

Boultwood

Bull

2019

ACS Omega

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“…6 Pioneering work in the formation of monochloroaziridines was reported by Deyrup and co-workers; a monochloroaziridine was generated by the reaction of dichloromethyllithium with N -benzylideneaniline at low temperatures, affording the cis -chloroaziridine (Figure 1A). 9a Since this seminal investigation, α-chloroaziridines have been accessed via reductive halogenation from gem -dihalogented aziridines, 10 addition of acid chlorides across 2 H -azirines, 11 nitrene addition to chloroalkenes, 12 and trapping of metalated aziridines with an electrophilic source of chlorine (Figure 1B). 13 Chlorinated aziridines have been shown to undergo nucleophilic displacement of chloride with a variety of nucleophiles including NaOMe, NaCN and LiAlH 4 , leaving the aziridine intact.…”

Section: Introductionmentioning

confidence: 99%

Synthesis ofcis-C-Iodo-N-Tosyl-Aziridines using Diiodomethyllithium: Reaction Optimization, Product Scope and Stability, and a Protocol for Selection of Stationary Phase for Chromatography

et al. 2013

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The preparation of C-iodo-N-Ts-aziridines with excellent cis-diastereoselectivity has been achieved in high yields by the addition of diiodomethyllithium to N-tosylimines and N-tosylimine–HSO2Tol adducts. This addition-cyclization protocol successfully provided a wide range of cis-iodoaziridines, including the first examples of alkyl-substituted iodoaziridines, with the reaction tolerating both aryl imines and alkyl imines. An ortho-chlorophenyl imine afforded a β-amino gem-diiodide under the optimized reaction conditions due to a postulated coordinated intermediate preventing cyclization. An effective protocol to assess the stability of the sensitive iodoaziridine functional group to chromatography was also developed. As a result of the judicious choice of stationary phase, the iodoaziridines could be purified by column chromatography; the use of deactivated basic alumina (activity IV) afforded high yield and purity. Rearrangements of electron-rich aryl-iodoaziridines have been promoted, selectively affording either novel α-iodo-N-Ts-imines or α-iodo-aldehydes in high yield.

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“…The present article reports on our first results of asymmetric synthesis of fluorinated DOI: 10.1134 prop-2-yn-1-amines from enantiomerically pure imines through chiral fluoroaziridines. Monofluoroaziridines can be obtained in different ways: by reaction of fluorocarbene with imines [33,34], by reduction of halofluoroaziridines with Bu 3 SnH [35,36], and by cyclization of β-fluoro-β-bromo(chloro) amines in the presence of bases [37,38]. The two latter procedures imply basic conditions, so that they are unsuitable for the synthesis of nonracemic compounds derived from amino acids.…”

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confidence: 99%

Monofluorinated aziridines in asymmetric synthesis of chiral fluorinated prop-2-yn-1-amines

et al. 2010

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Nonracemic C-fluoroaziridines were synthesized for the first time by reaction of fluorocarbene with N-diphenylmethylidene-substituted natural amino acid esters. The products were shown to be used in asymmetric synthesis of chiral fluorinated prop-2-yn-1-amines via one-pot process involving isomerization of 2-fluoroaziridines into α-fluoro imines and subsequent reaction with alkynyldifluoroborane generated in situ.Prop-2-yn-1-amines are widely used as medical agents for the treatment of various diseases [1-10] and as building blocks in the synthesis of polyfunctional nitrogen-containing organic compounds [11][12][13][14][15][16][17][18]. Development of convenient synthetic approaches to chiral prop-2-yn-1-amines [19][20][21][22][23][24][25] is an important problem, taking into account that the use of nonracemic drugs is one of the most important lines in modern medicine [26][27][28][29][30].We recently showed that fluorinated prop-2-yn-1-amines can readily be obtained by reaction of potassium arylethynyltrifluoroborates with 3-fluoro-2,2-diphenylaziridine in the presence of boron trifluorideether complex (Scheme 1) [31]. It was found that the formation of fluorinated prop-2-yn-1-amines from monofluoroaziridines involves Lewis acid-catalyzed isomerization of 2-fluoroaziridines into α-fluoro imines which then react with alkynyldifluoroborane. Acceleration of the process and reduction in the amount of by-products in the case of substrates containing a methoxycarbonylmethyl group (R = CH 2 CO 2 Me; A, R 1 = R 2 = H) was rationalized assuming formation of intermediate chelate A [31]. The formation of cyclic intermediate implies that addition of arylethynyl nucleophile at the C=N bond of substrates with a chiral carbon atom (C* in A, R 1 ≠ R 2 ) could occur with high diastereoselectivity due to rigidity of the transition state and proximity of the chiral center to the reaction center [32] (Scheme 1). Therefore, we presumed that the reaction sequence including isomerization of chiral aziridine and subsequent reaction of the imine thus formed with potassium alkynyltrifluoroborate should provide a simple and convenient synthetic route to chiral functionalized prop-2-yn-1-amines. The present article reports on our first results of asymmetric synthesis of fluorinated

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Reduction of 1,3-diphenyl-2,2-dihaloaziridines with tri-n-butyltin hydride

Cited by 30 publications

References 7 publications

Synthesis of Selenoaziridines: A Study on Stereochemical Outcomes of the Reaction of Aziridine Radicals and Anions Generated from Iodoaziridines

Synthesis of Selenoaziridines: A Study on Stereochemical Outcomes of the Reaction of Aziridine Radicals and Anions Generated from Iodoaziridines

Synthesis ofcis-C-Iodo-N-Tosyl-Aziridines using Diiodomethyllithium: Reaction Optimization, Product Scope and Stability, and a Protocol for Selection of Stationary Phase for Chromatography

Monofluorinated aziridines in asymmetric synthesis of chiral fluorinated prop-2-yn-1-amines

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