O-Alkyl oximes

Mn02, hexane or CH2CI2, it, 70-92% yield. " The oximes of pyruvates and O-alkyl oximes are not cleaved under these conditions. 

Aromatische O-Alkyl-oxime ergeben in ahnlicher Weise mit Natrium-cyano-trihydrido-borat die entsprechenden 0,N-Dialkyl-hydroxylamine z. B.2 ... 

O-Alkyl-oxime werden durch Diboran in siedendemTHF7oder langsamer bei 20°7 8 durch zwei Hydrid-Aquivalente in Amin und Alkohol gespalten. 

Natrium-trifluoracetoxy-trihydrido-borat reduziert O-Alkyl-oxime in siedendera Tetrahydrofuran zu prim. Aminen. So erhalt man z. B. aus O-Methyl-acetophenon-oxim 1 -Phenyl-dthylamin zu 90% d.Th.. ... 

Aqueous NaOH (10%, 5 ml) is added to the haloalkane (4 mmol) and TBA-Br (0.1 g, 0.3 mmol) in PhH (2 ml). The mixture is stirred for 20 h at room temperature and then diluted with Et20 (5 ml). The organic phase is separated, washed well with H20 and aqueous NH4CI (5%), dried (Na2S04), and evaporated to yield the O-alkyl oxime (Table 3.2). 

The isomerization of the (Z)-isomer into the ( )-isomer promoted by the iridium complex explains the lack of stereospecificity of the transformation. O-Alkylated oximes and ketoximes do not react and this fact suggests that the presence of both hydrogen and a hydroxyl group is required for the success of the transformation. The authors proposed that the initial displacement of a chloride ion of the iridium complex by the oxime allows the iridium to remove both the oxygen and the hydride from the initial oxime. Swapping places of both substituents produces the amide. 

Bei einem anderen Verfahren zur Herstellung von optisch-aktiven Aminoalkanen aus Oxim-Derivaten reduziertman O-Alkyl-oxime, deren Alkyl-Gruppe (evtl. auch funktionell substituiert) mit einem asymmetrischen C-Atom an die Hydroximino-Gruppe gebunden ist1. Auf diese Weise erhalt man z.B. durch Reduktion von chiralem Acetophenon-[0-(l-carboxy-ethyl)-oxim] mit Boran-Tetrahydrofuran (S)-1-Amino-1-phenyl-ethan in 72% chemischer Ausbeute und einem ee-Wert von 40%. 

The O-alkyl oximes of dialkyl mesoxalates have also been investigated361,362 the triazoline adducts undergo rapid decomposition at 20°C, at which reaction was performed, and give the required aziridines in 60-80% yields. Because of the presence of an ether substituent on the nitrogen, the oximes require two weeks for completion of reaction. O-Methyl ethers of acetoxime and biacetyl oxime do not react at all with diazomethane even after 3 months in ether at 20°C.361... 

Polyakov, V.A., Nelen, M.I., Nazarpack-Kandously, N., Ryabov, A.D., Eliseev, A.V. Imine exchange in O-aryl and O-alkyl oximes as a base reaction for aqueous dynamic combinatorial libraries. A kinetic and thermodynamic study. J. Phys. Org. Chem. 1999, 12, 357-363. 

O-Alkyl oximes are excellent precursors of COs as they react more slowly with ozone than alkenes. Initially <1995LA1571>, as added carbonyl species, acyl cyanides and esters of trifluoroacetic acid were used and the ozonides could be isolated usually in 25-60% yields. In an extension of this reaction, trapping could be performed by a variety of carbonyl compounds. 

Pr) were prepared in good yields from the corresponding O-alkyl oximes (eq. 8.35).73 Similarly, 2-alkoxyamino-l-(3- or 4-pyridyl)propanes were prepared in 22-73% yields from the corresponding O-alkyl methyl picolyl ketoximes. 

Both hydrazones and O-alkyl oximes of asymmetrical carbonyl compounds exist in two iso-... 

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