Publication:

A new method for stereoselective homoallylic amine synthesis (1993)

Author(s): Susan K. Armstrong;Eric W. Collington;Julian G. Knight;Alan Naylor;Stuart Warren

  • : A new method for stereoselective homoallylic amine synthesis

Abstract: Nitrile oxide cycloaddns. to readily available allylic diphenylphosphine oxides [Ph2P(O)CHR1CH:CH2; R1 = H, Me, Et, Pr, isobutyl] proceeded regioselectively and stereoselectively to give 5-(1'-diphenylphosphinoyalkyl)isoxazolines [I and II; R1 as above, R2 = Et, Pr, hexyl, Ph, Me, CO2Et,(CH2)nCO2Me, n = 2,3]. These heterocycles were reduced to d-amino-b-hydroxyalkyldiphenylphosphine oxides (III and IV; R1, R2 as above) using a combination of sodium borohydride and nickel(II) chloride. Stereospecific elimination of diphenylphosphinic acid from the redn. products using sodium hydride in N,N-dimethylformamide gave homoallylic primary amines (V and VI; R1, R2 as above) of defined stereochem. [on SciFinder (R)]

Notes: CAN 120:133786 23-4 Aliphatic Compounds Univ. Chem. Lab.,Cambridge,UK. Journal 0300-922X written in English. 7791-20-0 (Nickel dichloride hexahydrate) Role: CAT (Catalyst use), USES (Uses) (catalysts, for sodium borohydride stereoselective redn. of dihydroisoxazoles); 107-29-9 (Acetaldehyde oxime); 110-69-0 (Butyraldehyde oxime); 629-31-2 (Heptanal oxime); 932-90-1 (Benzaldehyde oxime); 13372-76-4 Role: PROC (Process) (nitrile oxide cycloaddn. of, to allylic diphenylphosphine oxides); 152972-33-3P; 152972-35-5P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and attempted nitrile oxide cycloaddn. of); 627-39-4P (Propanal oxime); 152972-36-6P; 152972-37-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and nitrile oxide cycloaddn. of, to allylic diphenylphosphine oxides); 136679-66-8P; 136679-67-9P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and regioselective nitrile oxide cycloaddn. of); 136679-70-4P; 136679-71-5P; 136679-72-6P; 136679-73-7P; 136679-74-8P; 136679-75-9P; 136679-76-0P; 136679-77-1P; 136679-84-0P; 136679-85-1P; 136679-86-2P; 136679-88-4P; 136679-89-5P; 152972-38-8P; 152972-39-9P; 152972-40-2P; 152972-41-3P; 152972-42-4P; 152972-43-5P; 152972-44-6P; 152972-45-7P; 152972-46-8P; 152972-47-9P; 152972-48-0P; 152972-49-1P; 152972-50-4P; 152972-51-5P; 152972-52-6P; 152972-53-7P; 152972-54-8P; 152972-55-9P; 152972-56-0P; 152972-57-1P; 152972-58-2P; 152972-59-3P; 152972-60-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and stereoselective redn. of); 136679-93-1P; 136679-94-2P; 136679-95-3P; 136679-96-4P; 136777-97-4P; 136777-98-5P; 136777-99-6P; 136778-00-2P; 136778-03-5P; 136778-04-6P; 136778-05-7P; 136778-06-8P; 136778-07-9P; 136778-08-0P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. in Horner-Wittig stereoselective reaction of); 136679-82-8P; 136679-99-7P; 136680-01-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. in stereoselective Horner-Wittig reaction of); 136680-00-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 1079-66-9 (Chlorodiphenylphosphine) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with allylic alc., allylic diphenylphosphine oxides from); 152972-34-4 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with chlorodiphenylphosphine, cyclopentylpropenyldiphenylphosphine oxide from); 2305-21-7 (2-Hexen-1-ol) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with chlorodiphenylphosphine, hexenyldiphenylphosphine oxide from); 77053-92-0 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with chlorodiphenylphosphine, methylhexenylidene phenylphosphine oxide from); 5362-55-0 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with chlorodiphenylphosphine, methylpentenyl diphenylphosphine oxide from); 103-71-9 (Phenyl isocyanate) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with phosphine oxide and Me nitrobutyrate, dihydroisoxazole from); 13013-02-0 (Methyl 4-nitrobutyrate) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with phosphine oxide and Ph isocyanate, dihydroisoxazole deriv. from); 14337-43-0 (Ethyl chlorooximidoacetate) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with phosphine oxide, triethylamine and dihydroisoxazole deriv. from); 4141-48-4; 13303-58-7; 63103-53-7 Role: PROC (Process) (regioselective nitrile oxide cycloaddn. of); 102879-25-4P; 136869-33-5P; 136869-34-6P; 152972-61-7P; 152972-62-8P; 152972-63-9P Role: RCT (Reactant), PREP (Preparation), RACT (Reactant or reagent) (stereoselective synthesis of)

  • Short Title: A new method for stereoselective homoallylic amine synthesis
  • Journal: Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999)
  • Issue: 13
  • Pages: 1433-47
  • Publication type: Article
  • Bibliographic status: Published

    Keywords: Sound and Ultrasound (effect of, on nitrile oxide cycloaddn. to allylic diphenylphosphine oxides); Stereochemistry (of Horner-Wittig reaction diphenylphosphinic acids); Regiochemistry (of nitrile oxide cycloaddns. to allylic diphenylphosphine oxides); Wittig reaction (Horner, stereoselective, for prepn. of homoallylic amines); Amines Role: RCT (Reactant), RACT (Reactant or reagent) (homoallylic, stereoselective synthesis of, new method for); Cycloaddition reaction (regioselective, of nitrile oxides to allylic diphenylphosphine oxides, ultrasound effect on); Reduction (stereoselective, (diphenylphosphinoylalkyl)isoxazolines) homoallylic amine stereoselective synthesis; Horner Wittig reaction stereoselective; cycloaddn nitrile oxide regioselective; diphenylphosphinic acid stereospecific elimination

    Staff

    Dr Julian Knight
    Senior Lecturer