A Micellar Iodide‐Catalyzed Synthesis of Unprotected Aziridines from Styrenes and Ammonia

Varszegi, Csaba; Ernst, Martin; Laar, Frederik van; Sels, Bert F.; Schwab, E.; Vos, Dirk De

doi:10.1002/ange.200704772

Cited by 6 publications

(4 citation statements)

References 39 publications

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“…However, a practical, functional group-tolerant and environmentally benign direct preparation of N-H aziridines from structurally diverse olefins has so far eluded synthetic chemists. (24–31) Herein, we report an operationally simple, inherently safe, chemoselective and stereospecific conversion of a wide range of olefins to the corresponding N-H/N-Me aziridines via a rhodium-catalyzed pathway free of external oxidants.…”

mentioning

confidence: 99%

Direct Stereospecific Synthesis of Unprotected N-H and N-Me Aziridines from Olefins

Jat

Paudyal

Gao

et al. 2014

Science

282

217

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Despite the prevalence of the N-H aziridine motif in bioactive natural products and the clear advantages of this unprotected parent structure over N-protected derivatives as a synthetic building block, no practical methods have emerged for direct synthesis of this compound class from unfunctionalized olefins. Here, we present a mild, versatile method for the direct stereospecific conversion of structurally diverse mono-, di-, tri- and tetra-substituted olefins to N-H aziridines using O-(2,4-dinitrophenyl)hydroxylamine (DPH) via homogeneous rhodium catalysis with no external oxidants. This method is operationally simple (i.e., one-pot), scalable and fast at ambient temperature, furnishing N-H aziridines in good-to-excellent yields. Likewise, N-alkyl aziridines are prepared from N-alkylated DPH derivatives. Quantum-mechanical calculations suggest a plausible Rh-nitrene pathway.

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mentioning

confidence: 99%

Direct Stereospecific Synthesis of Unprotected N-H and N-Me Aziridines from Olefins

Jat

Paudyal

Gao

et al. 2014

Science

282

217

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“…[23] Handling halide salts is safer and easier and they can be easily oxidized to the corresponding positive halogens or hypohalous acids by a variety of methods. [24] One method for this purpose is to use H 2 O 2 as an environmentally friendly and strong oxidant. [25] However, the rate of oxidation of halides with H 2 O 2 is slow and not a practical process.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Halogenation of Organic Compounds with Halides Catalyzed by Cerium(III) Chloride Heptahydrate Using Hydrogen Peroxide as the Terminal Oxidant in Water

et al. 2009

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In this article a new environmentally friendly catalytic method is described for the efficient monoiodination and bromination of arenes and also iodoetherification and iodolactonization of olefins using hydrogen peroxide as the terminal oxidant. The method is based on using sodium iodide or sodium bromide, hydrogen peroxide (35%) and ceriumA C H T U N G T R E N N U N G (III) chloride as an effective catalyst in water at room temperature or under reflux conditions. By this protocol, iodination of anilines proceeded with high regioselectivity at the para position with the formation of small amounts of the ortho isomers. However, bromination of anilines proceeded with absolute regioselectivity to give the para isomers as the sole products in high yields. Iodinations and brominations of m-xylene, toluene, chloro-and bromobenzenes were proceeded with excellent regioselectivity to produce the para isomers as the sole products. Benzene was also halogenated by this catalytic system to give the monohalogenated benzene in good yields. Iodoetherification and iodolactonization of olefins also proceeded easily in high yields at room temperature. However, the bromination of olefins by this protocol failed and the starting materials were detected intact.

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“…They have now demonstrated that DPH can be used in direct aziridination of olefins in the presence of a rhodium catalyst, [Rh 2 (esp) 2 ], which was first reported by Du Bois and coworkers. [11] This remarkable new reaction affords NH aziridines [12] using low catalyst loadings and only a slight excess of DPH while operating at ambient temperature in trifluoroethanol. Not only are the reaction conditions mild and catalytic, but equally important is the observation that this new aziridination reaction is stereospecific, with E olefins being cleanly converted into trans-NH aziridines and Z olefins into cis-NH aziridines.…”

mentioning

confidence: 99%

A Scalable Rhodium‐Catalyzed Intermolecular Aziridination Reaction

Smith¹,

Njardarson²

2014

Angew Chem Int Ed

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A Micellar Iodide‐Catalyzed Synthesis of Unprotected Aziridines from Styrenes and Ammonia

Cited by 6 publications

References 39 publications

Direct Stereospecific Synthesis of Unprotected N-H and N-Me Aziridines from Olefins

Direct Stereospecific Synthesis of Unprotected N-H and N-Me Aziridines from Olefins

Highly Efficient Halogenation of Organic Compounds with Halides Catalyzed by Cerium(III) Chloride Heptahydrate Using Hydrogen Peroxide as the Terminal Oxidant in Water

A Scalable Rhodium‐Catalyzed Intermolecular Aziridination Reaction

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