N-Allylcyclopentylideneamine置于lithium Aluminium Tetrahydride体系中,用 乙醚 作为反应溶剂,化学反应 4.0H,以87%的收率获得产物n-烯丙基环戊基胺
参考文献:Lewis Acid-Promoted 3-Aza-Cope Rearrangement Of N-Alkyl-N-Allyl Enamines
标题:Lewis Acid-Promoted 3-Aza-Cope Rearrangement Of N-Alkyl-N-Allyl Enamines
摘要:The 3-Aza-Cope Rearrangement Of The N-Alkyl-N-Allylenamines Derived From Isobutyraldehyde,Which Proceeds Thermally At 250-Degrees-C,Has Been Accelerated By A Variety Of Electrophilic Reagents To Give Gamma,Delta-Unsaturated Imines. Protic Acids,Such As Hcl (0.5 Equiv),And The Lewis Acidic Reagents Ticl4 (0.1-0.2 Equiv),Et2O.Bf3 (0.5 Equiv),And Alme3 (1.0 Equiv) Produced Complete [3,3] Rearrangement Of Substrates At 111-Degrees-C. By Increasing The Lewis Acidity Of The Aluminum Reagents,This Transformation Was Achieved At 50-Degrees-C With Clalme2,Cl2Alme,And Methylaluminum Bis(2,6-Diphenylphenoxide). Reaction Conditions Were Studied Initially By Glc Analysis Of The N-Isobutyl Derivative. These Optimum Conditions Were Then Used To Obtain Isolated Yields Of 59-99% For Rearrangement And In Situ Lialh4 Reduction Of The Analogous N-Methylcyclohexyl Substrate To The Corresponding Delta,Epsilon-Unsaturated Amine. Substrates Derived From 2-Phenylpropanal,N-Butanal,Cyclohexanone,And Cyclopentanone Were Used To Examine The General Effectiveness Of Hcl,Ticl4,And Alme3 As Reagents For Acceleration Of The [3,3] Rearrangement. The Most Versatile And Efficient Reagent For Promoting This Reaction,Alme3,Produced Overall Yields Of 83-96% For The Two-Step Rearrangement And Reduction Of These Substrates.
DOI:10.1021/jo00028A016