Ultramicromethods: VI. Lithium aluminum hydride reduction of aldehydes and ketones

The lithium aluminum hydride reduction of 1 ng of the aldehyde, decanal and of the ketone, 2-decanone is described. The method should be applicable to further classes of compounds amenable to reduction by complex hydrides.     

Evidence for single electron transfer in the reduction of alcoholswith lithium aluminum hydride

EPR evidence supporting a single electron transfer mechanism in the reduction of secondary and tertiary alcohols to hydrocarbons with LiAlH₄ is presented.     

Highly enantioselective reduction of ketones by chiral diol-modified lithium aluminum hydride reagents

Some readily available chiral diols from indene and d-mannitol were investigated as chiral modifiers in lithium aluminum hydride reduction of ketones, and it was discovered that further modification of these reducing reagents by a simple a-amino alcohol resulted in a remarkable increase in optical yield. Among the investigated chiral modifiers, chiral diol 1 gave the highest enantioselectivities.     

Reduction of diarylphthalides with aluminum lithium hydride

Conclusions The reduction of diarylphthalides with LiA1H₄ in THF leads to the corresponding diarylphthalans.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, p. 686, March, 1979.     

Peculiarities in the reduction ofα-bromoalkyl 4-hydroxy-3,5-di-tert-butylphenyl ketones with lithium aluminum hydride

Conclusions Hydrogenolysis of the carbonyl group and replacement of the bromine atom by the hydroxyl group occurs when-bromoalkyl 4-hydroxy-3,5-di-tert-butylphenyl ketones are reduced, with the formation of-alkyl-(4-hydroxy-3,5-di-tert-butylphenyl)ethyl alcohols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1391–1393, June, 1967.The authors wish to thank N. M. Emanuel for his constant interest in the present study while it was being carried out.     

Carboncarbon bond cleavage during lithium aluminum hydride reduction of a terminal propargyl alcohol

Reduction of dehydronerolidol with lithium aluminum hydride in the presence of sodium methoxide gave, in addition to the expected nerolidol, geranyl acetone. Labeling experiments established that the C-1 methyl of geranyl acetone is derived from one of the carbons of the acetylene.     

Organic Sonochemistry,ultrasonic acceleration of the reduction of simple and deactivated aryl halides using lithium aluminum hydride

Eleven aromatic halides are reduced in very high yields in the presence of LiAlH₄ and sonic waves at 35°.     

Stereoselective reduction of gem-dichlorocyclopropanes to cis-monochlorocyclopropanes by lithium aluminum hydride in the presence of titanium and zirconium complexes

A versatile stereoselective method is presented for the synthesis of cis-monochlorocyclopropanes by the reduction of dehalogenated alkyl- and aryl-gemdichlorocyclopropanes in the presence of catalytic quantities of titanium and zirconium complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2084–2087, September, 1991.     

Reductions of acetylenes and conjugated diolefins by lithium aluminum hydride

A convenient method is described for the stereospecific reduction of acetylenes by LAH. For example, 2-pentyne, 3-hexyne, 1-phenylpropyne and diphenylethyne in an ether solvent have been reduced to the corresponding trans olefin in high yield 2,4-Hexadiene was reduced in a similar manner to give a mixture of 2- and 3-hexenes. With toluene as the solvent, the main products from acetylenes are the saturated hydrocarbons. Whereas a trans addition of the hydride to the triple bond occurs in ether solvents, it appears that cis addition occurs in toluene.