Thermal decomposition of products of the addition of diisobutylaluminum hydride to nitriles

Summary In the thermal decomposition of the products of the addition of diisobutylaluminum hydride to nitriles RCH =NA1 (1-C₄H₉)₂, isobutene is liberated and the corresponding amines RCH₂H₂ are formed after hydrolysis of the residue.     

Reduction of methylcyclohexanones with diisobutylaluminum hydride

Summary The stereochemistry of the reduction of the 2-,3- and 4-methylcyclohexanones by diisobutylaluminum hydride was studied and it was found that in the case of 2-methylcyclohexanone the steric factor exerts an influence on the reduction course.     

Action of diisobutylaluminum hydride on enamines

Summary Diisobutylaluminum hydride adds to enamines with the formation of compounds containing the grouping , the thermal decomposition of which gives the corresponding olefins in good yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1695–1697, September, 1964     

Reduction of carboxylic esters to aldehydes with diisobutylaluminum hydride

Summary Some aliphatic and aromatic carboxylic esters were reduced to the corresponding aldehydes in high yield with diisobutylaluminum hydride at low temperature (–70°).     

Preparative synthesis of disilane from hexaethoxydisilane and diisobutylaluminum hydride

A preparative method for the synthesis of Si₂H₆ from Si₂(OEt)₆ and (i-Bu)₂AlH is developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 795–796, April, 1993.     

Hydroalumination of cycloolefins by diisobutylaluminum hydride catalyzed by zirconium compounds

Conclusions Zirconium chloroalkoxides are effective catalysts for the hydroalumination of cycloolefins by diisobutylaluminum hydride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 669–673, March, 1982.     

Tishchenko reactions and Oppenauer oxidation reactions of aldehydes promoted by diisobutylaluminum hydride

The aliphatic aldehydes react with catalytic amount of Dibal-H in n-pentane to give the corresponding Tishchenko products in good to excellent yields. Contrary, α-silyloxyaldehydes give α-silyloxyketones via Oppenauer oxidation under similar condition.     

Tishchenko reactions of aldehydes promoted by diisobutylaluminum hydride and its application to the macrocyclic lactone formation

Aliphatic aldehydes react with catalytic amount of Dibal-H in n-pentane to give the corresponding Tishchenko products in good to excellent yields. On contrary, α-silyloxy aldehydes give α-silyloxy ketones via Oppenauer oxidation under similar condition. Tishchenko reaction of ω-alkene aldehydes followed by RCM and hydrogenation affords a convenient method to prepare the 11-37 membered macrocyclic lactones.     

Stereocontrol in hydride addition to ketone-derived chiral N-acylhydrazones

Chiral N-acylhydrazones derived from various aldehydes and N-amino-4-benzyl-2-oxazolidinone have previously been shown to be effective for acyclic stereocontrol of intermolecular radical and allylsilane additions. Treatment of the propionaldehyde hydrazone with tributyltin hydride in the presence of boron trifluoride etherate led to rapid chemoselective reduction of the imine bond in high yield. Preparation of similar hydrazones from ketones led to E/Z isomer mixtures, usually in ratios of 4:1 or greater. Geometry of the CN bond was assigned by steric compression shifts in ¹³C NMR spectra. Reduction with tributyltin hydride and boron trifluoride etherate afforded diastereomer mixtures in ratios very similar to the original E/Z isomer ratios. The chiral auxiliary blocked the opposite face of the CN bond relative to a related process using a chelated Lewis acid. A stereocontrol model involving monodentate interaction of the N-acylhydrazone and boron trifluoride is consistent with the observed stereochemical outcome.     

A hammett correlation for the addition of organotin hydride to benzaldehydes

The relative rates for tri-n-butyltin hydride additions to substituted benzaldehydes under free radical and polar conditions have been determined from competitive reactions. The relative rates have been correlated by the Hammett σ or σ⁺ constants. The polar addition is correlated best by σ and the free radical addition by σ⁺. Interpretations of the results are presented.     

The role of hydrogen atoms in CIDNP effects in the reaction of diisobutylaluminum hydride with CCl4

Integral polarization of chloroform, methylene dichloride, and pentachloroethane was observed in the¹H NMR spectra during the exothermal reaction of a 1M solution of Bu₂ ⁱ in 1,4-dioxane with CCI₄. CIDNP was shown to appear in the diffusion radical pair of the hydrogen atom and trichloromethyl radical. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2097–2099, October, 1998.     

Intramolecular hydride addition to pyridinium salts: new routes to enantiopure dihydropyridones

The transformation of a simple disubstituted pyridine into a pyridinium ion bearing an exocyclic hydroxyl group, protected as a silane, enabled an intramolecular hydride transfer reaction to take place when fluoride was used as a nucleophile. The addition was both regio- and stereoselective and enabled the formation of enantiopure dihydropyridones when enantiopure pyridine derivatives were used in this sequence. The heterocyclic products contain ample functionality for further elaboration reactions and subsequent derivatization.     

Reduction of α - substituted succinonitriles with diisobutylaluminum hydride: a facile method for the synthesis of 3-substituted pyrroles

Treatment of four representative α - substituted succinonitriles (2) with diisobutylaluminum hydride, followed by hydrolysis of each reaction mixture with aqueous sodium dihydrogen phosphate, afforded 3-substituted pyrroles (4) in approximately 50% yield.