Lithium aluminum hydride-Copper iodide

Lithium-Ammonia, 234-236 Lithium-Ethylamine, 236 Lithium aluminum hydride, 236-237 Lithium aluminum hydride-Copper(I) iodide, 237... 

Related Reagents. Lithium Aluminum Hydride-(2,2 -Bipy-ridyl)(l,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-l, E-binaphthyl Lithium Aluminum Hydride-Chromium(III) Chloride Lithium Aluminum Hydride-Cobalt(II) Chloride Lithium Aluminum Hydride-Copper(I) Iodide Lithium Aluminum Hydride-Diphosphoms Tetraiodide Lithium Aluminum Hydride-Nickel(II) Chloride Lithium Aluminum Hydride-Titanium(IV) Chloride Titanium(III) Chloride-Lithium Aluminum Hydride. 

Triphenylstannane reduced the double bond in dehydro-)J-ionone in 84% yield [872], Complex copper hydrides prepared in situ from lithium aluminum hydride and cuprous iodide in tetrahydrofuran at 0° [873], or from lithium trimethoxyaluminum hydride or sodium bis(methoxy-ethoxy)aluminum hydride and cuprous bromide [874] in tetrahydrofuran at 0° reduced the a,p double bonds selectively in yields from 40 to 100%. Similar selectivity was found with a complex sodium bis(iron tetracarbonyl)hydride NaHFe2(CO)g [875]. 

Oppolzer has developed a method of asymmetric synthesis based on the use of the chiral auxiliaries 39A and 39B derived respectively from (+ )-camphor [(+ )-40] and (- )-camphor [(- )-40]. Crotonylation of 39A gave the ester that was attacked by 4-methyl-3-pentenyllithium in the presence of copper iodide tributylphosphine and boron trifluoride from only one side of the molecule, the product 41 having the (S)-configuration (enantioselectivity 98.5%). The ester 42—similarly obtainable from 39B—was methylated under similar conditions, also yielding 41 with 92% enantioselectivity. (S)-Citronellic acid [(S)-36] or (S)-citronellol [(S)-33] were then obtained from 41 by the action of sodium hydroxide or lithium aluminum hydride (Scheme 6). Reduction of potassium... 

ALKENES Allyl dimethyldithiocarbamate. Bis(t -cyclopentadienyl)niobium trihydride. Cyanogen bromide. Di-n-butylcopperlithium. a,o-Dichloromethyl methyl ether. 2,3-Dimethyl-2-butylborane. N,N-Dimethyl dichlorophosphoramide. Diphenyl diselenide. Di-n-propylcopperlithium. Ferric chloride. Grignard reagents. Iodine. Lithium phenylethynolate. Lithium 2,2,6,6-tetramethylpiperidide. Methyl iodide. o-Nitro-phenyl selenocyanate. Propargyl bromide. rra s-l-Propenyllithium. Selenium. Tetrakis(triphenylphosphine)palladium. Titanium(IH) chloride. Titanium trichloride-Lithium aluminum hydride. p-Toluenesulfonylhydrazine. Triphenylphosphine. Vinyl-copper reagents. Vinyllithium. Zinc. 

The cross-coupling reaction of 226 with a variety of aromatic halides proceeds without difficulty in triethylamine in the presence of bis(triphenylphosphine)palladium(II) chloride and copper(I) iodide under sonication conditions to furnish the corresponding arylacetylenes 229 in satisfactory yields. Refluxing these arylacetylenes with lithium aluminum hydride in THF provides in good yields the corresponding allylic alcohols 230 having the -config-uration [81]. 

The introduction of a polyfluorinated chain is not so easy as that of an alkyl chain. Transition metal catalyzed cross-coupling of Grignard reagents and organozinc compounds are inefficient in the synthesis of polyfluorinated 3-alkylthiophene. The copper-catalyzed perfluoroalkylation results in the formation of 2-and 3-substituted thiophenes, which are difficult to separate from each other. The reaction of fluorinated alkylmagnesium iodide with 3-formylthiophene, follwed by reduction with lithium aluminum hydride, gave (22) in an overall yield of 40% [27]. 

The second key building block, phosphonium salt 172, was prepared as outlined in Scheme 3.39. Iodide 163 was reacted in a copper(I)-catalyzed alkylation with the bisbromo-magnesium salt 164 to give triyne 165 in 90% yield. Reduction of the propargylic alcohol 165 to allylic alcohol 166 was achieved with lithium aluminum hydride (LAH), and then a... 

Chromic anhydride-pyridine, 70 Chromium hexacarbonyl, 71 Chromones, 423 Chromous chloride, 73 Chrysanthemic acid, 49, 50, 207-208 Chrysanthemic esters, 183-184 Cinnamic esters, 362 CitroneUol, 5, 308, 309 Claisen rearrangement, 2, 372 Clemmensen reduction, 426 Cocaine, 384 Codeine, 236, 347, 348 Conjugate addition, 86, 102, 119-120, 133, 226-227, 253, 353, 400 Cope rearrangement, 66, 397 Copper, 73-74 Copper(I) acetate, 80 Copper(II) acetate, 39, 117, 126, 186 Copper(I) bromide-Lithium trimethoxy-aluminum hydride, 80 Copper(I) bromide, 79-80 Copper(I) chloride, 50, 80-81 Copper(II) chloride, 126, 79 Copper(l) cyanoacetate, 74 Copper halide nitrosyls, 73 CopperO) iodide, 81-82 Copper(I) methyltrialkylborates, 4,75 CopperGD perchlorate. 79 COpper(I) phenylacetylide, 237 Copper(II) sulfate, 117 CopperO) trifluoiomethanesulfonate, 75-76... 

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