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Solubility: sol Et2O, THF, DME, HMPA; unstable above 0 °C in these solvents; stable in hexane or pentane (0.5-0.6 M) at rt for weeks, when not cooled or concentrated;10 the complex with one molecule of THF is soluble in alkanes like cyclohexane and heptane.
Form Supplied in: solid; 2.0 M solution in heptane/THF/ethylbenzene stabilized with Mg(i-Pr2N)2; 10 wt % suspension in hexanes; LDA.THF complex, 1.5 M solution in cyclohexane and 2.0 M in heptane.
Handling, Storage, and Precautions: very moisture- and air-sensitive, and should always be kept in an inert atmosphere; irritating to the skin and mucous membranes; therefore contact with skin, eyes, and other tissues and organs should be avoided; proper protection is necessary. Use in a fume hood.
Copper dienolates of a,b-unsaturated acids, prepared by Copper(I) Iodide transmetalation, can be selectively g-alkylated with allylic halides; the use of nonallylic electrophiles leads mainly to a-alkylation (eq 20).40 Copper enolates of a,b-unsaturated esters41 and amides42 show similar behavior.
Metalated t-butyl 2-t-butyl-2,5-dihydro-4-methoxyimidazole-1-carboxylate is alkylated in good yields and with high trans diastereoselectivity (>99:1); hydrolysis of the resulting adducts liberates the a-amino acid methyl esters in high yields (eq 25).57 Using this method, the (S)-t-butyl 2-t-butylimidazole derivative gave, upon isopropylation and hydrolysis, the L-valine methyl ester with 81% ee.
Lithiated furan- and thiophenecarboxylic acids (eq 56),114,115 indoles (eq 57),116 indole-3-carboxylic acids (eq 58),117 benzofurancarboxylic acids,118 and thiazole- and oxazolecarboxylic acids119 serve well in heteroaromatic synthesis.
Lithium Amide; Lithium Hexamethyldisilazide; Lithium Diethylamide; Lithium Piperidide; Lithium Pyrrolidide; Lithium 2,2,6,6-Tetramethylpiperidide; Potassium Diisopropylamide.
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