Oxime esters hydrides

Electrophilic Imine, Hydrazone, Oxime Ester as the Hydride Acceptors... 

Lithium aluminum hydride (LiAlH4) is the most powerful of the hydride reagents. It reduces acid chlorides, esters, lactones, acids, anhydrides, aldehydes, ketones and epoxides to alcohols amides, nitriles, imines and oximes to amines primary and secondary alkyl halides and toluenesulfonates to... 

Diisobutylaluminum phenylselenolate (39), which is prepared in situ by the reaction between diphenyl diselenide and diisobutylaluminum hydride (DIBALH) [67], is also a useful nucleophilic selenium reagent (Scheme 37). For example, 39 reacts with oxime sulfonates to produce selenoimidic esters... 

When dihydroisorubijervine is oxidized with chromic acid in acetic-sulfuric acid there is formed a keto carboxylic acid (XXIII) in which the keto group was demonstrated by the formation of an oxime and a semi-carbazone, and the carboxyl was demonstrated by the formation of a methyl ester (XXIV), whose reduction with lithium aluminum hydride regenerated dihydroisorubijervine (XVIII) (58). 

Oxime ethers derived from hydroxy aldehydes, upon conversion to their phenyl thionocarbonate esters, undergo radical cyclizations resulting in the formation of carbocycles. For example, an oxime ether obtained from D-glucose is converted into its phenyl thionocarbonate ester at C-5 and, upon heating in benzene in the presence of tributyltin hydride, affords cyclopentanes in 93% yield as a 62 38 mixture of two diastereomers (eq 7). In general, only low to modest stereoselectivity between the newly formed stereocenters is observed in a number of substrates examined. 

The anions of malonate esters, cyclopentadiene, -keto esters, ketones, " aldehydes, a-nitroacetate esters, Meldrum s acid, diethylaminophosphonate Schiff bases, -diketones, -sulfonyl ketones and esters, and polyketides represent the wide variety of carbon nucleophiles effective in this reaction. Generation of the stabilized anions normally is accomplished by addition of sodium hydride, potassium hydride, or basic alumina. However, when allyl substrates such as allylisoureas, allyl oxime carbonates, or allyl imidates are used, the allylation reaction proceeds... 

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