Iron chloride, reaction with lithium

Reaction of the lithium enolate 2 with prochiral aldehydes at low temperature proceeds with little selectivity, producing all four possible diastereomers 3, 4, 5, and 6 in similar amounts50. Transmetalation of the lithium enolate by treatment with three equivalents of diethylaluminum chloride or with one equivalent of copper cyanide generates the corresponding cthylaluminum and copper enolates which react at — 100°C with prochiral aldehydes to produce selectively diastereomers 1 and 2, respectively50. The reactivity of tin enolates of iron- propanoyl complexes has not been described. 

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

Acylmetallocenes undergo many reactions shown by acylbenzenes (35, 87, 91, 116, 124), but a detailed discussion is not presented here. Reductions with either lithium aluminum hydride or sodium borohydride give the corresponding carbinols, while Clemmensen reduction, reduction with lithium aluminum hydride plus aluminum chloride, catalytic hydrogenation, etc., yield corresponding alkyl derivatives. Acetylferrocenes undergo a variety of base condensation reactions and can be oxidized to ferrocenecarboxylic acids without apparent oxidation of the iron atom. 

The a-protons of iron acyl complexes are acidic and these can be deprotonated with Lithium diisopropylamide (LDA) or with n-butyllithimn. Thus the corresponding enolates are readily functionalized and undergo reaction with alkyl halides, aldehydes, disulfides, trimethylsilyl chloride, and epoxides to afford the corresponding a-derivatized products. " Early work on racemic complexes revealed that these transformations occur in a highly diastereoselective fashion,... 

Ignition on contact with furfuryl alcohol powdered metals (e.g., magnesium iron) wood. Violent reaction with aluminum isopropoxide -f- heavy metal salts charcoal coal dimethylphenylphosphine hydrogen selenide lithium tetrahydroaluminate metals (e.g., potassium, sodium, lithium) metal oxides (e.g., cobalt oxide, iron oxide, lead oxide, lead hydroxide, manganese oxide, mercur oxide, nickel oxide) metal salts (e.g., calcium permanganate) methanol + phosphoric acid 4-methyl-2,4,6-triazatricyclo [5.2.2.0 ] undeca-8-ene-3,5-dione + potassium hydroxide a-phenylselenoketones phosphorus phosphorus (V) oxide tin(II) chloride unsaturated organic compounds. 

In the absence of alcohol the reduction may be halted at the dihydro stage, but with difficulty. Stoichiometric control (3 equiv. of metal) gives reasonable results, but it seems to be most effective to use 5 equiv. of lithium with added iron(III) chloride. Thus, from the reduction of (112), quenching with ammonium chloride gives either the 1,2- or 1,4-dihydro products (114) and (115), respectively, while reaction with methyl iodide affords excellent yields of the 2-methyl-1,2-dihydro derivatives (113 Scheme 20). 

DIBAL-H/n-butyllithium, in cyclic and acyclic systems with iron pentacarbonyl, in cyclodecanes with lithium dihydrodimethoxyaluminate(III)/copper(I) iodide, and in cyclohexane and cyclopentane systems with NaH/sodium r-butylpentyl/Ni(OAc)2. ° The monoreduction of 1,3-diketones can be carried out under similar conditions, as illustrated by the reaction of a substituted cyclohexane-1,3-dione with oxalyl chloride to give the corresponding 1-chlorocyclohexenone, which was subsequently reduced to the enone with zinc-silver couple (Scheme 45). Kropp et al. have reported the photolytic reduction of vinyl iodides in acyclic systems however, when an a-hydrogen is present, formation of the diene product is a limiting side reaction (Scheme 46). For a more extensive discussion of vinyl halide reductions, see the preceding chapter in this volume. 

For the preparation of unsymmetrical ferrocenes, two ways by which only mono-substituted derivatives are produced have been suggested. One route starts from iron tetracarbonyl and a substituted cyclopenta-diene the other from monocyclopentadienyl iron dicarbonyl bromide, which on treatment with a substituted cyclopentadienyl lithium is finally converted into the corresponding mono-substituted ferrocene. Experience shows the first method to be more suitable for the preparation of aryl, and the latter method for the preparation of alkyl, derivatives (57). Corresponding work already carried out on substitution in Ru(C5H6)2 and Os CsH5)2 has also been fruitful. It is found that in the Friedel-Crafts reaction with acetyl or benzoyl chloride there is a distinct predominance of mono- over disubstitution as the atomic weight of the central atom increases (47, 72). 

The reaction of 2,3-bis( art-butylsulfanyl)cyclopropenethione (47) with lithium indenide in tet-rahydrofuran, followed by addition of tert-butyl chloride, proceeded to give the 5,6-disulfanyl-benzo[7)]calicene derivative 48, which was converted to the doubly cross-conjugated (1-cyclo-propenylideneinden-3-yl)cyclopropenylium derivative 49 by further reaction with l,2-bis(tc/ t-butylsulfanyl)-3,3-dichlorocyclopropene in the presence of iron(III) chloride and treatment with 70% perchloric acid. ... 

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