Reductive coupling Titanium chloride-Zinc

Solutions of low-valence titanium chloride (titanium dichloride) are prepared in situ by reduction of solutions of titanium trichloride in tetrahydrofuran or 1,2-dimethoxyethane with lithium aluminum hydride [204, 205], with lithium or potassium [206], with magnesium [207, 208] or with a zinc-copper couple [209,210]. Such solutions effect hydrogenolysis of halogens [208], deoxygenation of epoxides [204] and reduction of aldehydes and ketones to alkenes [205,... 

Reductive coupling of carbonyls to alkenes Titanium(IV) chloride-Zinc, 310 of carbonyls to pinacols Titanium(III) chloride, 302 Titanium(IV) chloride-Zinc, 310 of other substrates Samarium(II) iodide, 270 Reductive cyclization 2-(Phenylseleno)acrylonitrile, 244 Tributylgermane, 313 Tributyltin hydride, 316 Triphenyltin hydride, 335 Trityl perchlorate, 339 Reductive hydrolysis (see Hydrolysis) Reductive silylation Chlorotrimethylsilane-Zinc, 82... 

Reductive coupling of carbonyl groups Titanium(IV) chloride-Zinc, 310 From three-membered heterocycles Arylselenocarboxamides, 22 Titanium(IV) chloride-Lithium aluminum hydride, 310... 

Mukaiyama, T., Sato, T., Hanna, J. Reductive coupling of carbonyl compounds to pinacols and olefins using titanium(IV) chloride and zinc. Chem. Lett. 1973, 1041-1044. 

Alkenes can be obtained from aldehydes or ketones on reductive dimerization by treatment with a reagent prepared from titanium(III) chloride and zinc-copper couple (or L1A1H4), or with a species of active titanium metal formed by reduction of titanium(III) chloride with potassium or lithium metal. This McMurry coupling reaction is of wide application, but in intermolecular reactions generally affords a mixture of the E- and Z-alkenes (2.99). 

The pinacol (94) was also obtained by reductive dimerization of retinaldehyde (2) with zinc amalgam (Reedy, 1968) or in the presence of chromium(III) salts (Sopher and Utley, 1979). With a mixture of lithium aluminum hydride and titanium chloride in anhydrous tetrahydrofuran, retinaldehyde (2) underwent reductive coupling to give p-carotene (Akiyama et al., 1979 Mukaiyama, 1977 McMurry et al., 1978 Ishida and Mukaiyama, 1977). 

A third method for the synthesis of cycl[3.2.2]azines, from iV-(aroylmethyl)pyridinium salts via indolizines, involves intramolecular (reductive) McMurry coupling of the latter. For example, 3,5-dibenzoylindolizines, obtained from 2-benzoyl-iV-phenacylpyridinium bromide as shown (Scheme 91), are cyclized using zinc and titanium(iv) chloride to give the 3,4-diphenylcyclazines 352 in high yield (>90%). The reaction cannot be applied, however, to... 

Lithium butyldimethylzincate, 221 Lithium sec-butyldimethylzincate, 221 Organolithium reagents, 94 Organotitanium reagents, 213 Palladium(II) chloride, 234 Titanium(III) chloride-Diisobutylalu-minum hydride, 303 Tributyltin chloride, 315 Tributyl(trimethylsilyl)tin, 212 3-Trimethylsilyl-l, 2-butadiene, 305 Zinc-copper couple, 348 Intramolecular conjugate additions Alkylaluminum halides, 5 Potassium t-butoxide, 252 Tetrabutylammonium fluoride, 11 Titanium(IV) chloride, 304 Zirconium(IV) propoxide, 352 Miscellaneous reactions 2-(Phenylseleno)acrylonitrile, 244 9-(Phenylseleno)-9-borabicyclo[3.3.1]-nonane, 245 Quina alkaloids, 264 Tributyltin hydride, 316 Conjugate reduction (see Reduction reactions)... 

Since the introduction of the titanocene chloride dimer 67a to radical chemistry, much attention has been paid to render these reactions catalytic. This field was reviewed especially thoroughly for epoxides as substrates [123, 124, 142-145] so only catalyzed reactions using non-epoxide precursors and a few very recent examples of titanium-catalyzed epoxide-based cyclization reactions, which illustrate the principle, will be discussed here. A very useful feature of these reactions is that their rate constants were determined very recently [146], The reductive catalytic radical generation using 67a is not limited to epoxides. Oxetanes can also act as suitable precursors as demonstrated by pinacol couplings and reductive dimerizations [147]. Moreover, 5 mol% of 67a can serve as a catalyst for the 1,4-reduction of a, p-un saturated carbonyl compounds to ketones using zinc in the presence of triethylamine hydrochloride to regenerate the catalyst [148]. 

Titanium (iv) chloride with zinc in pyridine has been found to couple ketones reductively to afford symmetrical tetrasubstituted ethenes. Unsymmetrical alkenes can be synthesized in useful yields by titanium-induced ketone coupling if the less reactive component is used in excess. Cycloalkenes (ring size 4—16) are prepared in good yield by intramolecular coupling of the corresponding alkanedione. ... 

The inline conversion of nitrate to nitrite and subsequent spectrophotometric determination after diazotization and coupling reactions is the basis of an important set of analytical methods for the simultaneous determination of both ions. Either homogeneous (titanium(III) chloride, hydrazinium sulfate, etc.) or heterogeneous (zinc, cadmium, amalgamated cadmium, copperized cadmium, etc.) reduction agents, photochemical or enzymatic reactions have been used [157]. The nitrite so produced is determined through spectrophotometric detection of the reddish purple azo dye formed as a result of the modihed Griess chemistry. 

Titanium(iii) chloride and HCl provide a means of reduction of a,a-dibromo-ketones to the corresponding a-chloro-compounds [equation (50)]. ° a,a -Dibromo-ketones are reduced to a-acetoxy-ketones by ultrasonically dispersed mercury in acetic acid. A wide variety of dienes react with a,a -dibromo-ketones in the presence of a zinc-silver couple or an iron carbonyP in the [3 + 4 - 7] sense to give cyclohept-4-enones [equation (51)]. 

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