Epoxides and Aziridines from Diazoacetates via Ylide Intermediates

Doyle, Michael P.; Hu, Wenhao; Timmons, Daren J.

doi:10.1021/ol015600x

Cited by 167 publications

(67 citation statements)

References 9 publications

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“…This methodology has also been described for oxonium ylides, which have been shown to undergo nucleophilic addition with a range of electrophiles, including aldehydes and activated ketones. 523 353,622 and hydride transfer 502 (Scheme 266). The 1,3-dipolar cycloaddition is the most common reaction pathway and is the focus of this section.…”

Section: [12]-stevens Rearrangementmentioning

confidence: 99%

Modern Organic Synthesis with α-Diazocarbonyl Compounds

Ford¹,

Miel

Ring³

et al. 2015

Chem. Rev.

1,312

585

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Section: [12]-stevens Rearrangementmentioning

confidence: 99%

Modern Organic Synthesis with α-Diazocarbonyl Compounds

Ford¹,

Miel

Ring³

et al. 2015

Chem. Rev.

1,312

585

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“…Two recent reports on addition of diazoacetates to aldehydes have emerged (compare Scheme 9.15). Rhodium(ii) acetate catalyzes this addition, giving trisubstituted vinylepoxides in good yields [64,65].…”

Section: Vinylepoxides From Aldehydesmentioning

confidence: 99%

Vinylepoxides in Organic Synthesis

Olofsson

Somfai

2006

Aziridines and Epoxides in Organic Synthesis

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“…According to Doyle et al [17], N-benzylideneanilines under analogous conditions give rise to aziridines with cis orientation of the aryl groups in positions 2 and 3. For comparison, we synthesized methyl cis-1,2,3-triphenylaziridine-2-carboxylate (XIV) whose steric structure was determined [17] by X-ray analysis; however, its 1 H NMR spectrum was not reported. On the basis of the spectral data, compounds XII and XIII were assigned the structure with cis-oriented aromatic substituents.…”

mentioning

confidence: 99%

New Tandem Reactions of Metal Carbenoids. Intermolecular Formation of Azomethine Ylide from Methyl 2-Diazo-2-phenylacetate and Schiff Base: Intramolecular 1,3-Dipolar Cycloaddition

et al. 2005

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Rhodium acetate-catalyzed decomposition of methyl 2-diazo-2-phenylacetate in the presence of substituted N-methylbenzylideneamines possessing an activated alkenyl fragment (dipolarophile) in the side chain gives products of intramolecular cycloaddition of intermediate Z,E-and E,Z-azomethine ylides. The cycloaddition is regioselective, and the products are hexahydrochromeno[4,3-b]pyrrole derivatives. The stereoselectivity of the process depends on the temperature. In the temperature range from 20 to 80°C, the major stereoisomer is that with cis junction of the tetrahydropyran and pyrrolidine rings. N-Phenylazomethine ylides generated from methyl 2-diazo-2-phenylacetate and alkyl 4-[2-(phenyliminomethyl)phenoxy]-2-butenoates at 40°C undergo cyclization to aziridines at a higher rate, as compared to the rate of cycloaddition to the internal dipolarophile. N-Phenylazomethine ylides generated by thermolysis of the corresponding aziridine or by the "deprotonation" method react with equal regio-and stereoselectivity to give intramolecular cycloaddition products, hexahydrochromeno[4,3-b]pyrrole derivatives with trans-fused tetrahydropyran and pyrrolidine rings. Analysis of the experimental and calculation data suggests preference of the endo transition state in the cycloaddition of the examined azomethine ylides. Intramolecular 1,3-dipolar cycloadditions of azomethine ylides underlie effective procedures for the synthesis of various fused, bridged, and cage-like polycyclic nitrogen-containing compounds [1]. An important problem is the stereoselectivity of cycloaddition of ylide intermediates, for it determines the efficiency of this approach as applied to a particular synthetic task. Low stereoselectivity often results from configurational heterogeneity of ylide intermediate owing to fairly severe conditions of its generation [2][3][4]. The stereoselectivity problem may be solved by development of such methods for generation of azomethine ylides which would allow their geometry to be controlled. One of these methods is based on reactions of carbenes or carbenoids with compounds possessing a C=N bond and is referred to as "carbene" technique. These reactions occur as a rule under mild conditions, and they make it possible to generate ylides which cannot be obtained by other methods [5].The synthetic sequence intermolecular carbene generation of azomethine ylide-intramolecular cycloaddition almost was not studied as a method of synthesis of nitrogen-containing polycyclic compounds. Only recently, we described examples of such syntheses with the use of difluorocarbene and dichlorocarbene [6][7][8].The goal of the present study was to develop approaches to tandem synthesis of fused heterocycles via the above reaction sequence involving carbenoids generated from diazo compounds. As model system we used azomethine ylides generated by addition of carbene-like species derived from methyl 2-diazo-2-phenylacetate to N-methyl-and N-phenylbenzylideneamines I-IV possessing an activated alkenyl fragment (dipolarophile) in the ortho po...

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Epoxides and Aziridines from Diazoacetates via Ylide Intermediates

Abstract: An effective methodology is reported for stereospecific epoxidation and aziridination via carbonyl ylide intermediates using rhodium(II) acetate catalyzed reactions of phenyl- and styryldiazoacetates with aldehydes, ketones, or imines.

Cited by 167 publications

References 9 publications

Modern Organic Synthesis with α-Diazocarbonyl Compounds

Modern Organic Synthesis with α-Diazocarbonyl Compounds

Vinylepoxides in Organic Synthesis

New Tandem Reactions of Metal Carbenoids. Intermolecular Formation of Azomethine Ylide from Methyl 2-Diazo-2-phenylacetate and Schiff Base: Intramolecular 1,3-Dipolar Cycloaddition

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