13657-16-4Relevant articles and documents
Direct synthesis of N-substituted 1,3-oxazolidines via a hetero-domino Petasis borono-Mannich reaction of 1,2-amino alcohols, formaldehyde, and organoboronic acids
Zheng, Yiting,Sun, Lu,Wang, Jiayi,Song, Gonghua
, p. 648 - 653 (2019/08/07)
[Figure not available: see fulltext.] A simple and convenient approach to the synthesis of N-substituted 1,3-oxazolidines via a hetero-domino Petasis borono-Mannich reaction of 1,2-amino alcohols, formaldehyde, and organoboronic acids has been reported. T
Electrooxidative cyclization of hydroxyamino compounds possessing a benzyl group
Okimoto, Mitsuhiro,Ohashi, Kousuke,Yamamori, Haruki,Nishikawa, Shinnosuke,Hoshi, Masayuki,Yoshida, Takashi
experimental part, p. 1315 - 1322 (2012/06/30)
Several novel 2-aryl-1,3-oxazinane and 2-aryl-1,3-oxazolidine derivatives were synthesized from N-benzyl-2-piperidineethanols and N-benzyl-2- piperidinemethanols, respectively, by using electrooxidative methods in methanol. For these reactions, the yields of the corresponding cyclized compounds were significantly increased by using catalytic amounts of iodide ions. In contrast, 3-dialkylamino-1-phenylpropanols afforded the expected cyclic 6-phenyl-1,3-oxazinane derivatives using only a small excess of base. Georg Thieme Verlag Stuttgart · New York.
Efficient synthesis of NK1 receptor antagonist aprepitant using a crystallization-induced diastereoselective transformation
Brands, Karel M. J.,Payack, Joseph F.,Rosen, Jonathan D.,Nelson, Todd D.,Candelario, Alexander,Huffman, Mark A.,Zhao, Matthew M.,Li, Jing,Craig, Bridgette,Song, Zhiguo J.,Tschaen, David M.,Hansen, Karl,Devine, Paul N.,Pye, Philip J.,Rossen, Kai,Dormer, Peter G.,Reamer, Robert A.,Welch, Christopher J.,Mathre, David J.,Tsou, Nancy N.,McNamara, James M.,Reider, Paul J.
, p. 2129 - 2135 (2007/10/03)
An efficient stereoselective synthesis of the orally active NK1 receptor antagonist Aprepitant is described. A direct condensation of N-benzyl ethanolamine with glyoxylic acid yielded a 2-hydroxy-1,4-oxazin-3-one which was activated as the corresponding trifluoroacetate. A Lewis acid mediated coupling with enantiopure (R)-1-(3,5-bis(trifluoromethyl)phenyl)ethan-1-ol afforded a 1:1 mixture of acetal diastereomers which was converted into a single isomer via a novel crystallization-induced asymmetric transformation. The resulting 1,4-oxazin-3-one was converted via a unique and highly stereoselective one-pot process to the desired α-(fluorophenyl)morpholine derivative. Interesting and unexpected [1,2]-Wittig and [1,3]-sigmatropic rearrangements were identified during the optimization of these key steps. In the final step, a triazolinone side chain was appended to the morpholine core. The targeted clinical candidate was thus obtained in 55% overall yield over the longest linear sequence.
The functionalisation of electron rich aromatic compounds with 1,3-oxazolidines and 1,3-dimethylimidazolidine
Heaney, Harry,Papageorgiou, George,Wilkins, Robert F.
, p. 14381 - 14396 (2007/10/03)
N-Phenyl- and N-alkyl-oxazolidines react with alkyl chlorosilanes in the presence of electron rich aromatic compounds with the formation of the expected Mannich bases: 2-methoxycarbonyl-3-methyloxazolidine also reacts with 2-methylfuran in the presence of thionyl chloride to give an a-amino acid derivative: the iminium salt derived from 1,3-dimethylimidazolidine was also shown to react with 2-methylfuran.
Formation of azomethine ylids by thermolysis of oxazolidines. Study of the reaction in solution and in the gaseous phase
Bureau, R.,Mortier, J.,Joucla, M.
, p. 584 - 596 (2007/10/02)
Thermolysis of oxazolidines leads to azomethine ylids via cycloreversion.In the liquid phase, these intermediates then give 1-3 dipolar cycloaddition; in the gaseous phase, they lead to aziridines.With an alkyl group in position 2, we observed also the formation of enamines.The effect of substituents on both the cycloreversion reaction and the evolution of azomethine ylids was studied.The mechanism of the process tautomerism aziridine -> azomethine ylid -> enamine is discussed.Keywords - azomethine ylids / oxazolidines / cycloreversion / aziridines / enamines / tautomerism
Parent and N-substitued azomethine ylides from α-amino acids and formaldehyde. An easy access to 2,5-unsubstituted pyrrolidines. Evidence for oxazolidin-5-ones as direct precursor of these reactive intermediates
Joucla, Marc,Mortier, Jacques
, p. 579 - 583 (2007/10/02)
Formaldehyde reacts with α-amino acids and electron deficient alkenes to produce pyrrolidines.Azomethine ylides involved as intermediates in these reactions have been generated from isolated oxazolidin-5-ones which can be considered as the direct precursors of these ylides.
On the Use of N-amino Ethers as Capped Azomethine Ylide Equivalents
Padwa, Albert,Dent, William
, p. 235 - 244 (2007/10/02)
N-amino ethers have been found to act as azomethine ylide equivalents.Treatment of these compounds with lithium fluoride in the presence of a reactive dipolarophile afforded dipolar cycloadducts in high yield.The cycloaddition proceeded with complete stereospecificity with dimethyl fumarate and maleate.This result is consistent with the intermediacy of an azomethine ylide.The reaction of N-benzyl-N-(methoxymethyl)-N-amine afforded several silylated diamines when treated with zinc chloride or cesium fluoride in the absence of trapping agent.This can be attributed to an initial loss of the methoxy group to give a transient iminium ion.This species reacts further with the azomethine ylide or undergoes hydrolysis to give a silylated amine.The cycloaddition behavior of several unsymmetrically substituted azomethine ylide precursors was also examined.Competitive rate studies showed that the cycloaddition is compatible with a HOMO-controlled process.The regiochemistry of the cycloaddition, however, is not easily rationalized by simple FMO considerations and may instead be related to the charge transfer interaction energy of the reaction.
