Trimethyl lithium

C10H15N, Benzenemethanamine, N,N,4-trimethyl-, lithium complex, 26 152 C10H15P, Phosphine, diethylphenyl-, nickel complex, 28 101 platinum complex, 28 135 CioHigAsi, Arsine, 1,2-phenylenebis(dimethyl-, gold complex, 26 89 nickel complex, 28 103 CioHie, 1,3-Cyclopentadiene, 1,2,3,4,5-pen-tamethyl-, 28 317 chromium complex, 27 69 cobalt complexes, 28 273, 275 iridium complex, 27 19 samarium complex, 27 155 titanium complex, 27 62 ytterbium complex, 27 148 CioH,gBrN04S, Bicyclo[2.2.1]heptane-7-methanesulfonate, 3-bromo-1,7-di-methyl-2-oxo-, U.IRHENDO, ANTPi]-, ammonium, 26 24... 

NCiqHis, Benzenemethanamine, N,N,2-trimethyl, lithium complex, 26 153 NCjjH, Pyridine, 2-(phenylmethyl)-palladium complex, 26 208-210 NCjjHis, Naphthalenamine, N,lV-dimethyl-, lithium complex, 26 154 NC13H9, Benzo[/i]quinoline, ruthenium complex, 26 177... 

J. Rebek, Jr., (1987) first developed a new synthesis of Kemp s acid and then extensively explored its application in model studies. The synthesis involves the straightforward hydrogenation (A. Steitz, 1968), esterification and methylation of inexpensive 1,3,5-benzenetricar-boxylic acid (trimesic acid 30/100 g). The methylation of the trimethyl ester with dimethyl sulfate, mediated by lithium diisopropylamide (V. J. Shiner, 1981), produced mainly the desired aff-cis-1,3,5-trimethyl isomer, which was saponified to give Kemp s acid. 

Aminoalkoxy pentaerythritols are obtained by reduction of the cyanoethoxy species obtained from the reaction between acrylonitrile, pentaerythritol, and lithium hydroxide in aqueous solution. Hydrogen in toluene over a mthenium catalyst in the presence of ammonia is used (34). The corresponding aminophenoxyalkyl derivatives of pentaerythritol and trimethyl olpropane can also be prepared (35). 

Phenylstibine [58266-50-5] C H Sb, has been obtained by the reduction of phenyldiio do stihine [68972-61-2] CgH3l2Sb, (73) or phenyldichlorostibine [5035-52-9] 031130.2, (74) with lithium borohydride. It has also been prepared by the hydrolysis or methanolysis of phenylbis(trimethylsilyl)stibine [82363-95-9] C22H23Si2Sb (75). Diphenylstibine [5865-81-6] C22H22Sb, can be prepared by the interaction of diphenylchlorostibine [2629-47-2] C22H2QClSb, with either Hthium borohydride (76) or lithium aluminum hydride (77). It is also formed by hydrolysis or methanolysis of diphenyl (trimethylsilyl)stibine [69561-88-2] C H SbSi (75). Dimesitylstibine [121810-02-4] h.3.s been obtained by the protonation of lithium dimesityl stibide with trimethyl ammonium chloride (78). The x-ray crystal stmcture of this secondary stibine has also been reported. 

To 1 g of 2j5-azido-3a-iodo-5a-cholestane ° in 10 ml benzene is added 0.4 g trimethyl phosphite. A boiling chip is added and the mixture allowed to stand at room temperature for 4 days. The solvent is removed in vacuo, with most of the trimethyl phosphite being removed at 0.1 mm. This crude product (100) is dissolved in 10 ml of dry ether and added dropwise to a stirred mixture of 0.5 g of lithium aluminum hydride in 10 ml of ether. After stirring at 25° for 3 hr, the excess of hydride is destroyed by the addition of 2 ml 20 % sodium hydroxide and the aluminum salts are filtered. The solution is washed with ether, and the ether removed in vacuo giving 0.71 g [76 %] of product (95) mp 101-103°. 

Homoesermetol (1,4a,9-trimethyl-6-methoxy-1,2,3,4,4a, 9a-hexa-hydro-a-carboline (89 R = CH3, R = OCH3) may be prepared in a manner analogous to that used for the preparation of eseroline. Thus, when the 3-y-oxindolylpropylamine 88 (R = CH3, R = OCH3) is reduced with sodium in butanol, homoesermetol is obtained. Reductive cycbzation of 88 (R = R = H) with lithium aluminum hydride has recently been reported. 

Heating 3,4-bis(phenylsulfonyl)furoxan with a solution of sodium butoxide in butanol followed by reduction with trimethyl phosphite gives furazan 281 (Scheme 183). Compound 281 was converted into dialkoxy derivative 282 with the lithium salt of ( )-l-azabicyclo[2.2.2]octan-3-ol in 33% overall yield (96W012711, 97EUP773021, 98JMC379). 

The nucleophilic acylation of 2-phenylpropanal or 3-phenyI-2-butanone with cyano(trimethyl-silyloxy)phenylmethyllithium proceeds with high Cram selectivity6. The primary addition product 7, after silyl migration and loss of lithium cyanide, gives the a-silyloxy ketones 86. 

Racemic [l-(4-methylphenylsulfinyl)-2-propenyl]lithium, prepared with lithium diiso-propylamide in THF, adds to racemic chiral 2-methylalkanals with good a- and syn selectivity114, us Qn heating with trimethyl phosphite or triethylamine, the major isomer furnishes the ( )-.yvn-2-alkene-l,4-diol by Mislow rearrangement1 lb. 

The reagents prepared by lithiation (see Section 1.3.3.3.1.2.) and titanium exchange of (S)-(Z)-l-methyl-2-butenyl diisopropylcarbamate106 show a diminished reactivity when compared with those derived from the ( -isomer, indicating that in both metalation steps the doublebond geometry is retained16. After treatment of the lithium -TMEDA complex with chlorotris-(diethylamino)titanium and 2-methylpropanal, the homoaldol adduct (3S,47f)-(Z)-4-hydroxy-1,3,5-trimethyl-l-hexenyl diisopropylcarbamate [( + )-4], is formed with 88% ee16. 

The aldol reaction of 2,2-dimethyl-3-pentanone, which is mediated by chiral lithium amide bases, is another route for the formation of nonracemic aldols. Indeed, (lS,2S)-l-hydroxy-2,4,4-trimethyl-l-phenyl-3-pentanone (21) is obtained in 68% ee, if the chiral lithiated amide (/ )-A-isopropyl-n-lithio-2-methoxy-l-phenylethanamine is used in order to chelate the (Z)-lithium cnolate, and which thus promotes the addition to benzaldehyde in an enantioselective manner. No anti-adduct is formed25. 

The reactions of the lithium enolates of substituted 2-cyclohexenones and 2-cyclopentenones with ( )-l-nitropropene give a mixture of syn- and ami-products3. The lithium enolate of 3,5,5-trimethyl-2-cyclohexenone gives a mixture of the syn- and //-3.5,5-trimethyl-6-(l-methyl-2-nitroethyl)-2-cyclohexcnoncs in modest diastereoselection when the reaction mixture is quenched with acetic acid after. 30 minutes at —78 =C. When the reaction mixture is heated to reflux, tricyclic products are obtained resulting from intramolecular Michael addition of the intermediate nitronate ion to the enone moiety. 

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