- Synthesis of β-prolinols via [3+2] cycloaddition and one-pot programmed reduction: Valuable building blocks for polyheterocycles
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A novel two-step synthesis of multisubstituted β-prolinols has been developed, featuring a [3+2] cycloaddition of azomethine ylides and a programmed reduction triggered by the combination of borane and lithium aluminum hydride (LAH). β-Prolinols are shown to be valuable building blocks for polyheterocycles.
- Li, Jundong,Lin, Na,Yu, Lei,Zhang, Yandong
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supporting information
p. 5777 - 5780
(2016/12/06)
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- The Cyano Group as a Traceless Activation Group for the Intermolecular [3+2] Cycloaddition of Azomethine Ylides: A Five-Step Synthesis of (±)-Isoretronecanol
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The cyano group was used as a traceless activation group for the [3+2] cycloaddition of azomethine ylides in a two-step process, thereby providing a highly effective approach to 5-unsubstituted pyrrolidines. The transformation includes the silver acetate
- Li, Jundong,Zhao, Huaibo,Jiang, Xunjin,Wang, Xiance,Hu, Haiming,Yu, Lei,Zhang, Yandong
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supporting information
p. 6306 - 6310
(2015/05/20)
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- Silver-catalyzed dynamic systemic resolution of α-iminonitriles in a 1,3-dipolar cycloaddition process
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A dynamic azomethine ylide system was established using Sc(OTf)3 and Ag/Taniaphos as catalysts. The system was subsequently kinetically resolved in a tandem 1,3-dipolar cycloaddition process where the silver complex acted as both a reaction catalyst and an external selector, resulting in the formation of an exclusive pyrrolidine product in good yield and enantiopurity. This journal is the Partner Organisations 2014.
- Hu, Lei,Ramstroem, Olof
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supporting information
p. 3792 - 3794
(2014/04/03)
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- Flash vacuum thermolysis generation and a UV-photoelectron spectroscopy study of the N-substituted iminoacetonitriles
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Flash vacuum thermolysis of cis and trans 1-benzyl and 1-allyl-2-cyano-3-phenylzetidines (1a and 1b) at 470 °C resulted in the formation of E and Z isomers of N-benzyl and N-allyl iminoacetonitriles 2a and 2b, respectively, beside small amounts of product
- Chrostowska, Anna,Dargelos, Alain,Graciaa, Alain,Khayar, Sa?d,Le?niak, Stanis?aw,Nazarski, Ryszard B.,Nguyen, Thi Xuan Mai,Maciejczyk, Ma?gorzata,Rachwalski, Micha?
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experimental part
p. 9322 - 9327
(2010/01/06)
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- The synthesis of alkyl aryl nitriles from N-(1-arylalkylidene)-cyanomethylamines. Part 2. Mechanism
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The mechanism of the rearrangement of N-(1-arylalkylidene)cyanomethylamines ArC(=NCH2CN)R 1 to the corresponding nitriles ArCH(CN)R2 (in DMF, at 150°C, with K2CO3) is described. Reaction 1 → 2 was investigated for different types of imine 1, and it was found that with a leaving group other than CN- the reaction does not proceed to yield the nitrile, whereas imines such as PhC(=NCH2CN)H, prepared starting from aldehydes rather than ketones, yield the expected phenylacetonitrile even at temperatures as low as 120°C. Evidence for the mechanism comes from a study of the reactivity of the postulated intermediates: 2-cyano-3-phenylaziridine 4c, and 2,2-diphenyl-2H-azirine 5b. The route involving aziridine 4c is ruled out, since this compound does not react at all under the investigated conditions. The 2H-azirine 5b instead, yields the corresponding diphenylacetonitrile in DMF with K2CO3, at 150°C. The transformation seems to involve an initial deprotonation, followed by an intramolecular ring closure-CN elimination step, which yields the 2H-azirine. The azirine then isomerizes to the nitrile. Additional evidence for the intermediacy of the 2H-azirine, based on 1H NMR monitoring of the reaction 1 → 2, is described. Finally, the results of a simple isotope exchange experiment provide a rationale for the previously observed scrambling of labels, and further confirm the proposed mechanism.
- Perosa, Alvise,Selva, Maurizio,Tundo, Pietro
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p. 1033 - 1037
(2007/10/03)
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- Efficient synthesis of N-alkylformimidoyl cyanides
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N-Alkylformimidoyl cyanides (RRCHN=CHCN, 1) were obtained through a very efficient oxidation of N-alkylaminoacetonitriles (RRCHNHCH2CN, 2) by aq. NaOCl. The reaction was run under very mild and simple conditions and afforded products (as E/Z isomer mixtures; E/Z ratio of 70-99%) in short reaction times (30-180 min), and in good to excellent yields (67-97%).
- Perosa, Alvise,Selva, Maurizio,Tundo, Pietro
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p. 7573 - 7576
(2007/10/03)
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