79405-36-0Relevant academic research and scientific papers
Cobalt(II)-Catalyzed Conversion of Allylic Alcohols/Acetates to Allylic Amides in the Presence of Nitriles
Mukhopadhyay, Manoj,Reddy, M. Madhava,Maikap, G. C.,Iqbal, Javed
, p. 2670 - 2676 (2007/10/02)
Various secondary allylic alcohols or their acetates and tertiary allylic alcohols can be converted to the corresponding transposed allylic amides in the presence of a catalytic quantity of cobalt(II) chloride and acetic anhydride in acetonitrile.Tertiary alcohols undergo complete rearrangement whereas secondary ones afford a mixture of regioisomers.Moderate yields of amides are also obtained by reacting acrylonitrile with secondary alcohols in 1,2-dichloroethane.The presence of acetic anhydride or acetic acid is crucial to the formation of amides as the absence of the former affords no amides and the allylic alcohols are mainly recovered as regioisomeric mixtures.The regioselectivity during amide formation can be enhanced by using cobalt complexes 14-16 in acetic acid medium.Some preliminary studies indicate that these reactions are proceeding via an ?-allyl complex or tight ion pair rather than a sigmatropic rearrangement of acetamidate obtained in a Pinner reaction.
Me5Cu3Li2: A Reagent for Conjugate Methylation of α,β-Unsaturated Aldehydes
Clive, Derrick L.J.,Farina, Vittorio,Beaulieu, Pierre L.
, p. 2572 - 2582 (2007/10/02)
Me5Cu3Li2, in ether or ether-pentane mixtures, converts α,β-unsaturated aldehydes efficiently into β-methyl aldehydes.In many cases of synthetic interest the amount of 1,2-methylation is negligible, and the reagent is far superior to Me2CuLi for conjugate methylation of enals.The performance of Me5Cu3Li2 is poor in sterically demanding situations, however.Several cuprate species were evaluated but none works as well as Me5Cu3Li2.For example, citral undergoes conjugate methylation with Me5Cu3Li2 in 80percent yield, and the product contains less than 0.5percent of 1,2-adduct.With Me2CuLi the product contains 10percent of 1,2-adduct.
Conjugate Addition of Methyl Groups to αβ-Unsaturated Aldehydes: Use of Me5Cu3Li2
Clive, Derrick L. J.,Farina, Vittorio,Beaulieu, Pierre
, p. 643 - 644 (2007/10/02)
Me5Cu3Li2 converts αβ-unsaturated aldehydes efficiently into β-methyl aldehydes and, unlike Me2CuLi, it usually gives a negligible amount of the 1,2-adduct even when a quaternary carbon is generated in the reaction.
