Neighboring‐Group Participation in Nitrile‐Forming Beckmann Fragmentation Reactions: Synthesis of Enantiopure (<i>E</i>)‐2,3‐Di‐<i>O</i>‐substituted‐5‐methoxy‐ pent‐4‐enenitriles and Their Conversion into Pyranosylamines

Passacantilli, Pietro; Centore, Clara; Ciliberti, Elena; Piancatelli, Giovanni; Leonelli, Francesca

doi:10.1002/ejoc.200400498

Cited by 11 publications

References 31 publications

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Beckmann Rearrangement and Beckmann Fragmentation

2010

Comprehensive Organic Name Reactions and Reagents

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The rearrangement of an oxime to its corresponding amide in the presence of an acid and is generally known as the Beckmann rearrangement. The oxime is also formed by the reaction of a ketone with hydroxylamine. The conversion of cyclohexanone oxime into e‐caprolactam is known to be an important component for the fabrication of nylon 6. The Beckmann rearrangement of oxime derivatives proceeds stereospecifically, and the stereo‐configuration of the migrating group is retained. This rearrangement has been applied to the construction of a variety of nitrogen‐containing compounds. Certain oximes, those having a quarternary carbon anti to the hydroxyl, have been reported to undergo the rearrangement to form nitriles instead of amides. This type of transformation is called the Beckmann fragmentation, which has been used in modification of steroids. Other oximes, such as the bridged bicyclic ketoximes and oximes with an electron‐donating substituent at the α‐carbon, also undergo fragmentation.

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Beckmann Rearrangement and Beckmann Fragmentation

2010

Comprehensive Organic Name Reactions and Reagents

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Rearrangements of Hydroxylamines, Oximes and Hydroxamic Acids

Pereira

Santos²

2010

Patai's Chemistry of Functional Groups

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Introduction The [3,3]‐Sigmatropic Rearrangements The [2,3]‐Sigmatropic Rearrangements The Dyotropic Rearrangements The B amberger Rearrangements The B eckmann Rearrangements The N eber Rearrangements The L ossen Rearrangement Other Rearrangements

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A Highly Efficient and Stereocontrolled Synthesis of 2‐Deoxy‐1,5‐thioanhydro‐L‐hexitols from D‐Glycals in a Tandem Nucleophilic Displacement Reaction

Passacantilli¹,

Centore²,

Ciliberti³

et al. 2006

Eur J Org Chem

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2-Deoxy-1,5-thioanhydro-L-hexitols have been synthesized in a concise sequence that includes: i) ring opening of glycals with aqueous mercury(II) acetate/sodium borohydride; ii) mesylation of the free hydroxy groups of the multifunctionalized open intermediates; and iii) S-heterocyclization by treatment with sodium sulfide. The thiosugar derivatives are obtained with a 60-80 % yield. Thus, D-glucal and D-galactal can be converted into the corresponding 2-deoxy-1,5-thioanhydro-L-hexitols, while L-rhamnal gives 3,4-di-O-benzyl-2,6-dide-

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Neighboring‐Group Participation in Nitrile‐Forming Beckmann Fragmentation Reactions: Synthesis of Enantiopure (E)‐2,3‐Di‐O‐substituted‐5‐methoxy‐ pent‐4‐enenitriles and Their Conversion into Pyranosylamines

Cited by 11 publications

References 31 publications

Beckmann Rearrangement and Beckmann Fragmentation

Beckmann Rearrangement and Beckmann Fragmentation

Rearrangements of Hydroxylamines, Oximes and Hydroxamic Acids

A Highly Efficient and Stereocontrolled Synthesis of 2‐Deoxy‐1,5‐thioanhydro‐L‐hexitols from D‐Glycals in a Tandem Nucleophilic Displacement Reaction

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