Synthesis and reactions of cyclopentadiene monoaziridine: a concise approach to the core of agelastatin A

Baron, Elise; O’Brien, Peter; Towers, Timothy D.

doi:10.1016/s0040-4039(01)02238-9

Cited by 46 publications

(19 citation statements)

References 24 publications

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“…En route to agelastatin A, O'Brien devised a strategy starting from cyclopentadiene. 33 Application of optimal conditions, i.e. 2 equivalents of diene, the reaction was conducted between 0°C and room temperature for a short period of time, then led to the expected compound 15 with a very good yield of 88%.…”

Section: Natural Product Synthesismentioning

confidence: 99%

Iminoiodanes and C-NBond Formation in Organic Synthesis

Dauban¹,

Dodd²

2003

Synlett

278

129

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Structurally related to iodosylbenzene PhI=O, iodonium imides PhI=NR, off-white to pale yellow solids of low solubility, belong to the class of hypervalent iodine(III) reagents and were first prepared nearly thirty years ago. Two additional decades were needed before they could be considered as useful nitrene precursors with the discovery of the copper-catalyzed aziridination of olefins. Since then, iminoiodanes have been successfully applied in the total synthesis of natural and/or biologically active compounds. Recent developments aimed at circumventing their tedious preparation led to the discovery of one-pot nitrogen transfers from sulfonamides, sulfamates, or carbamates mediated by iodosylbenzene(diacetate) PhI(OAc) 2 or iodosylbenzene. Reliable functionalizations of alkanes and alkenes via C-H insertion or aziridination using copper or rhodium catalysts can now be considered as synthetically useful processes.

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Section: Natural Product Synthesismentioning

confidence: 99%

Iminoiodanes and C-NBond Formation in Organic Synthesis

Dauban¹,

Dodd²

2003

Synlett

278

129

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“…7,8 Alternatively, different iodinanes PhI=NSO 2 R in combination with Cu(I) or Cu(II) salts can be used in the direct aziridination of alkenes, 9 and we have exploited this in previous studies. 8,10,11 Some different iodinanes were prepared by Andersson and co-workers 12 and Protasiewicz and co-workers; 13 the iodinanes can also be generated in situ, as reported by Dauban and Dodd. 14 In addition, N-SES-protected (SES: trimethylsilylethylsulfonyl) aziridines have been prepared using this approach.…”

Section: Figurementioning

confidence: 95%

Two-Step Synthesis ofN-Sulfonyl Aziridines from Epoxides

Huang¹,

O’Brien²

2006

Synthesis

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A convenient and high-yielding two-step synthesis of Nsulfonyl aziridines starting from epoxides is described. The method, which involves epoxide ring opening with sulfonamides and subsequent mesylation-cyclisation, is particularly suitable for variation of the N-sulfonyl substituent; 18 examples are presented.Aziridines have an ever-improving reputation as useful intermediates in synthetic organic chemistry. 1 As such, several different approaches and methodologies have been developed for the synthesis of aziridines. 1-3 With reference to the preparation of N-sulfonyl aziridines, close inspection of the different approaches reveals that they mostly generate N-toluenesulfonyl (N-tosyl) aziridines. Methodology for the synthesis of 'non-tosyl' aziridines is far less developed and/or typically low yielding. We are interested in developing new organolithium-mediated reactions of aziridines and our previous work has focused on the use of N-tosyl aziridines. 4,5 With a view to investigating other N-sulfonyl aziridines in the organolithium chemistry, we needed a reliable, high yielding and simple route to a range of N-sulfonyl aziridines 1 and 2 ( Figure 1). Figure 1The most straightforward route to N-sulfonyl aziridines 1 and 2 would be sulfonylation of the NH aziridine, which can be produced by Staudinger reduction of the azido alcohol (generated by ring opening of the corresponding epoxide). 6 In our hands, this three-step route is often lowyielding. 7,8 Alternatively, different iodinanes PhI=NSO 2 R in combination with Cu(I) or Cu(II) salts can be used in the direct aziridination of alkenes, 9 and we have exploited this in previous studies. 8,10,11 Some different iodinanes were prepared by Andersson and co-workers 12 and Protasiewicz and co-workers; 13 the iodinanes can also be generated in situ, as reported by Dauban and Dodd. 14 In addition, N-SES-protected (SES: trimethylsilylethylsulfonyl) aziridines have been prepared using this approach. 15 Overall, however, the iodinane methodology mostly employs PhI=NTs, is generally moderate to low yielding, and often works best with an excess of the alkene. N-Sulfonyl aziridines can also be prepared from alkenes using electrophilic Br + and N-chloramine sulfonamide salts (RSO 2 NCl -Na + ), as pioneered by Sharpless 16 and Komatsu. 17 These reactions almost always use commercially available chloramine-T 4,5,7,16-18 (introduction of an N-tosyl group), but Sharpless and co-workers have also used tBuSO 2 NCl -Na + . 19 Finally, three-step routes from epoxides to N-sulfonyl aziridines via epoxide ring opening using sulfonamides, activation, and cyclisation have been reported by Albanese 20 and Jacobsen. 21 Although both routes had not varied the sulfonamide significantly, the Albanese route appeared ideal for our purposes of generating a range of N-sulfonyl aziridines 1 and 2 from the corresponding epoxides. 22,23 The general approach we have optimised is summarised in Scheme 1. In particular, we have streamlined this approach into a two-step synthesis by cyclising the crude a...

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“…An alternative synthetic strategy, the direct aziridination of dienes by treatment with nitrido complexes [29] or PhI=NTs, [30,31] occurs with low regio-and chemoselectivities.…”

Section: Introductionmentioning

confidence: 99%

The [Ru(CO)(porphyrin)]‐Catalyzed Synthesis of N‐Aryl‐2‐vinylaziridines

et al. 2007

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[Ru(CO)(porphyrin)] complexes have been found to catalyze the direct aziridination of conjugated dienes by aryl azides with high chemoselectivity, to provide N-aryl-2-vinylaziridines. To determine the scope of the reaction, several hydrocarbons and azides were tested. The reactions between 2,3-dimethylbuta-1,3-diene and aryl azides bearing electronwithdrawing groups in the para or meta positions in their aryl moieties occur very efficiently in short times, while the selectivities of the aziridinations are governed by the steric hindrances of the double bonds, so lower yields are regis-

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Synthesis and reactions of cyclopentadiene monoaziridine: a concise approach to the core of agelastatin A

Cited by 46 publications

References 24 publications

Iminoiodanes and C-NBond Formation in Organic Synthesis

Iminoiodanes and C-NBond Formation in Organic Synthesis

Two-Step Synthesis ofN-Sulfonyl Aziridines from Epoxides

The [Ru(CO)(porphyrin)]‐Catalyzed Synthesis of N‐Aryl‐2‐vinylaziridines

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