Direct regiospecific allylic amination via silicon induced pericyclic reactions

Déléris, Gérard; Dunoguès, J.; Gadras, A.

doi:10.1016/s0040-4020(01)86670-9

Cited by 37 publications

(8 citation statements)

References 28 publications

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“…Allylic amines have become interesting targets for synthetic organic chemistry due to the presence of this functionality in several naturally occurring compounds . The usefulness of these compounds in organic synthesis is well documented . Procedures to synthesize allylic amines generally involve more than one reaction stage and use very specific catalysts .…”

Section: Resultsmentioning

confidence: 99%

“…[32][33][34][35] The usefulness of these compounds in organic synthesis is well documented. [36][37][38][39] Procedures to synthesize allylic amines generally involve more than one reaction stage and use very specific catalysts. [40] In this context, the reactive behaviour of all previously analysed alkylammonium-based PILs were tested against 2-methyl-1,3butadiene (4) (isoprene).…”

Section: Reactive Behaviours Of Pils With Non-polar Reactantsmentioning

confidence: 99%

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Understanding the Role of Protic Ionic Liquids (PILs) in Reactive Systems: Rational Selection of PILs for the Design of Green Synthesis Strategies for Allylic Amines and β‐Amino Esters

et al. 2019

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The reactive behaviour of protic ionic liquids (PILs) has been shown to be governed not only by their chemical structures but also by their global compositions, which include the presence of free acids and bases at equilibrium with ionic pairs. Six PILs composed of primary, secondary, or tertiary alkyl ammonium cations with two couterions, nitrate or acetate, were tested in model reactions with unsaturated substrates. The free species that were naturally present in these liquids were identified by cyclic voltammetry. Only tributylammonium nitrate was found to be mostly composed just of the ionic pair; the other five PILs also contain variable amounts of free acid and amine. In reactive systems, these free species determine the products of the reaction. In particular, allylic amines and β‐amino esters were obtained in good yields (91 and 75 %, respectively) by reaction of conjugated dienes and acrylates in the presence of PILs. By taking into account the actual composition of each PIL, it was possible to direct the reaction path towards a specific product with good yields, to ensure acid catalysis, to avoid polymerization of the substrate, and to promote phase transfer of products. These results establish some useful guidelines for the rational design of new PIL‐based one‐step synthetic strategies.

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Section: Resultsmentioning

confidence: 99%

Section: Reactive Behaviours Of Pils With Non-polar Reactantsmentioning

confidence: 99%

Understanding the Role of Protic Ionic Liquids (PILs) in Reactive Systems: Rational Selection of PILs for the Design of Green Synthesis Strategies for Allylic Amines and β‐Amino Esters

et al. 2019

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“…The iodozinc derivative of (126) prepared in three steps from the protected L-glutamic acid (125) has been reported to undergo coupling with a range of substituted aryl iodides to afford enantiopure g-aryl substituted GABA (127) derivatives in moderate to good yields (Scheme 14.36) [115,116].…”

Section: Baclofen and Analogsmentioning

confidence: 99%

“…The adduct (149) undergoes a [2,3] sigmatropic rearrangement on silylation. The resulting allylamine derivative (150) can then be converted to vigabatrin (2) by deprotection in 26.5% overall yield [125]. Ethyl 6-hydroxyhex-4-enoate (152), prepared in three steps from erythritol (151), undergoes an Overman rearrangement on heating in trichloromethyl acetimidate, introducing the amine functionality (Scheme 14.43).…”

Section: Baclofen and Analogsmentioning

confidence: 99%