86983-97-3Relevant academic research and scientific papers
Practical Chemoselective Acylation: Organocatalytic Chemodivergent Esterification and Amidation of Amino Alcohols with N-Carbonylimidazoles
Brown, Hailee,Heller, Stephen T.,Light, Christina,Medlin, Abigail,Nelson, Hope,Richard, William
supporting information, p. 22818 - 22825 (2021/09/13)
Chemoselective transformations are a cornerstone of efficient organic synthesis; however, achieving this goal for even simple transformations, such as acylation reactions, is often a challenge. We report that N-carbonylimidazoles enable catalytic chemodivergent aniline or alcohol acylation in the presence of pyridinium ions or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. Both acylation reactions display high and broad chemoselectivity for the target group. Unprecedented levels of chemoselectivity were observed in the DBU-catalyzed esterification: A single esterification product was obtained from a molecule containing primary aniline, alcohol, phenol, secondary amide, and N?H indole groups. These acylation reactions are highly practical as they involve only readily available, inexpensive, and relatively safe reagents; can be performed on a multigram scale; and can be used on carboxylic acids directly by in situ formation of the acylimidazole electrophile.
Radical and Ionic Nucleophilic Substitution Reactions on α-Alkyl-γ-(p-nitrophenyl)allyl Derivatives
Barker, Steven D.,Norris, Robert K.
, p. 527 - 544 (2007/10/02)
The nature of the reaction between α-alkyl-γ-(p-nitrophenyl)allyl chlorides (1)-(3), which have the general form p-O2NC6H4CH=CHCH(Cl)R, and a variety of nucleophiles depends on the alkyl group R and the nucleophile.The chloride (1) (R = Me) undergoes ionic (SN2 and subsequent Michael addition) processes with the salt (7) of 2-nitropropane to give products (15) and (16) whereas the chloride (2) (R = Pri) gives a mixture of products (17) and (18) which are shown to arise by a radical-chain nucleophilic substitution process, with allylic rearrangement-an SRN1' reaction- and ionic processes respectively.The chloride (3) (R = But) gives the SRN1' product (25) with the salt (7).Other nucleophiles with (2) and (3) appear to react by ionic (SN2 and SN2') and/or SRN1' processes; e.g. (3) gives an excellent yield of the malononitrile (32) by an SN2' process when treated with the sodium salt (9).
