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Physical Data: mp 125 °C; d 0.917 g cm-3.
Solubility: sol ether (35 g/100 mL; conc of more dil soln necessary); sol THF (13 g/100 mL); modestly sol other ethers; reacts violently with H2O and protic solvents.
Form Supplied in: colorless or gray solid; 0.5-1 M solution in diglyme, 1,2-dimethoxyethane, ether, or tetrahydrofuran; the LiAlH4.2THF complex is available as a 1 M solution in toluene.
Handling, Storage, and Precautions: the dry solid and solutions are highly flammable and must be stored in the absence of moisture. Cans or bottles of LiAlH4 should be flushed with N2 and kept tightly sealed to preclude contact with oxygen and moisture. Lumps should be crushed only in a glove bag or dry box.
The powerful hydride transfer properties of this reagent cause ready reaction to occur with aldehydes, ketones, esters, lactones, carboxylic acids, anhydrides, and epoxides to give alcohols, and with amides, iminium ions, nitriles, and aliphatic nitro compounds to give amines. Several methods of workup for these reductions are available. A strongly recommended option4 involves careful successive dropwise addition to the mixture containing n grams of LiAlH4 of n mL of H2O, n mL of 15% NaOH solution, and 3n mL of H2O. These conditions provide a dry granular inorganic precipitate that is easy to rinse and filter. More simply, solid Glauber's salt (Na2SO4.10H2O) can be added portionwise until the salts become white.5 In certain instances, an acidic workup (10% H2SO4) may prove advantageous because the inorganic salts become solubilized in the aqueous phase.6 Should water not be compatible with the product, the use of ethyl acetate is warranted since the ethanol that is liberated usually does not interfere with the isolation.4 Although the stoichiometry of LiAlH4 reactions is well established,1 excess amounts of the reagent are often employed (perhaps to make accommodation for the perceived presence of adventitious moisture). This practice is wasteful of reagent, complicates workup, and generally should be avoided.
When comparison is made between LiAlH4 and related reducing agents containing active Al-H and B-H bonds, LiAlH4 is seen to be the most broadly effective (Table 1).1h Its superior reducing power is also reflected in its speed of hydride transfer.
Epoxide Cleavage and Aziridine Ring Formation.
If a chiral adjuvant is used to achieve asymmetric induction, it should preferentially be inexpensive, easily removed, efficiently recovered, and capable of inducing high stereoselectivity.53 Of these, 1,3-oxathianes based on (+)-camphor66 or (+)-pulegone,67 and proline-derived 1,3-diamines,68 have been accorded the greatest attention.
For a more detailed discussion of asymmetric induction by this means, see also the following entries that deal specifically with LiAlH4/additive combinations.
Lithium Aluminum Hydride-(2,2�-Bipyridyl)(1,5-cyclooctadiene)nickel; Lithium Aluminum Hydride-Bis(cyclopentadienyl)nickel; Lithium Aluminum Hydride-Boron Trifluoride Etherate; Lithium Aluminum Hydride-Cerium(III) Chloride; Lithium Aluminum Hydride-2,2�-Dihydroxy-1,1�-binaphthyl; Lithium Aluminum Hydride-Chromium(III) Chloride; Lithium Aluminum Hydride-Cobalt(II) Chloride; Lithium Aluminum Hydride-Copper(I) Iodide; Lithium Aluminum Hydride-Diphosphorus Tetraiodide; Lithium Aluminum Hydride-Nickel(II) Chloride; Lithium Aluminum Hydride-Titanium(IV) Chloride; Titanium(III) Chloride-Lithium Aluminum Hydride.
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