165683-43-2Relevant academic research and scientific papers
Formal α-Allylation of Primary Amines by a Dearomative, Palladium-Catalyzed Umpolung Allylation of N-(Aryloxy)imines
Mori-Quiroz, Luis M.,Londhe, Shrikant S.,Clift, Michael D.
, p. 14827 - 14846 (2020/12/02)
N-(Aryloxy)imines, readily accessible by condensation/tautomerization of (pseudo)benzylic primary amines and 2,6-di-tert-butyl-1,4-benzoquinone, undergo efficient allylation to afford a wide range of homoallylic primary amines following hydrolytic workup. Deprotonation of N-(aryloxy)imines generates a delocalized 2-azaallyl anion-type nucleophile that engages in dearomative C-C bond-forming reactions with allylpalladium(II) electrophiles generated from allylic tert-butyl carbonates. This reactivity umpolung enables the formal α-allylation of (pseudo)benzylic primary amines. Mechanistic studies reveal that the apparent regioselectivity of the desired bond-forming event is a convergent process that is initiated by unselective allylation of N-(aryloxy)imines to give several regioisomeric species, which subsequently rearrange via stepwise [1,3]- or concerted [3,3]-sigmatropic shifts, ultimately converging to provide the desired regioisomer of the amine products.
Stereocontrolled synthesis of homoallylic amines using phosphine oxides and isoxazolines
Armstrong, Susan K.,Warren, Stuart,Collington, Eric W.,Naylor, Alan
, p. 4171 - 4174 (2007/10/02)
Allylic diphenylphosphine oxides (7) undergo stereo selective 1,3-dipolar cycloadditions with nitrile oxides to give Δ2-isoxazolines (8). These may be reduced, also stereoselectively, to δ-amino-β-hydroxyalkyldiphenylphosphine oxides (9). Stereospecific Wittig-Horner type elimination of Ph2PO2-from amino alcohols (9) gives homoallylic amines (10) with controlled double bond geometry.
