Some Unexpected Reactions in the Synthesis of 1-Phenyl-2-aminopropane-1,3-diol Starting from Phenyl β-Chlorovinyl Ketone

polymer crystallized from melt or solution [1OJ. Occasionally a less stable or low temperature structure can be produced. An example is the polycaprolactam made by zone polymerization which has not the ideal orthorhombic crystal structure, but a paracrystalline structure which has a less perfect alignment of Hbonds[331. The metaphosphates can be produced in a low temperature crystal form first which converts into the high temperature modification at higher temperature 31. Polyoxymethylene may under certain conditions of crystallization during polymerization form orthorhombic instead of hexagonal crystals 1121. Poly-p-xylylene also crystallizes during polymerization first as a metastable orthorhombic structure, to change at about 240 "C into the stable, denser hexagonal crystal structure "91.

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Addition of HO‐Acids to N,N‐Bis(oxy)enamines: Mechanism, Scope and Application to the Synthesis of Pharmaceuticals

Naumovich

Golovanov

Sukhorukov

et al. 2017

Eur J Org Chem

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The regioselectivity of the addition of HO‐acids to the activated π bond in N,N‐bis(oxy)enamines has been found to be dramatically dependent upon the solvent. Mechanistic investigations and quantum‐chemical calculations revealed that solvent affects the reaction pathway. In basic solvents (DMF, NMP, DMSO), N,N‐bis(oxy)enamines were converted into nitrosoalkenes by a Lewis base promoted process followed by oxy‐Michael addition of the HO‐acid. In non‐polar solvents (toluene, CH2Cl2), the reaction occurs by an acid‐promoted SN′ substitution of the N‐oxy‐group via a highly reactive N‐vinyl‐N‐alkoxynitrenium species. Based on these studies, general and efficient protocols for the oximinoalkylation of various HO‐acids (carboxylic acids, phenols, hydroxamic, phosphoric and sulfonic acids) employing readily available N,N‐bis(oxy)enamines were developed. These methods proved to be applicable to the post‐modification of natural molecules bearing acidic OH groups (such as steroidal hormones, bile acids, protected amino acids and peptides) and ligands (BINOL). The resulting α‐oxyoximes were demonstrated to be useful precursors of valuable 1,2‐amino alcohol or 1,2‐hydroxylamino alcohol derivatives, including the antiarrhythmic drug Mexiletine and a potent matrix metalloproteinase inhibitor.

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Some Unexpected Reactions in the Synthesis of 1-Phenyl-2-aminopropane-1,3-diol Starting from Phenyl β-Chlorovinyl Ketone

Cited by 5 publications

References 7 publications

Gabriel‐Synthese primärer Amine

Gabriel‐Synthese primärer Amine

The Gabriel Synthesis of Primary Amines

Addition of HO‐Acids to N,N‐Bis(oxy)enamines: Mechanism, Scope and Application to the Synthesis of Pharmaceuticals

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