Titanium tetrachloride lithium aluminum hydride

The Schmidt reaction affords both possible isomers when applied at the sulfide oxidation level, and also with the sulfoxide, no trace of sulfoximine being found (75CJC276). Reduction of the oxime to the amine with lithium aluminum hydride is significantly improved by the presence of titanium tetrachloride (78KGS1694). 

Examples of hydrogenolysis of aryl chlorides by lithium aluminum hydride are rare. Chlorobenzene is reduced to benzene only in a low yield, but chloronaphthalene gives a good yield of naphthalene with lithium aluminum hydride in the presence of either di-r-butyl peroxide or titanium tetrachloride (equation 51 ). ... 

Reduction of aryl bromides with lithium aluminum hydride takes place in tetrahydrofuran solutions at room temperature. It has also been performed with bener results in the presence of di-r-butyl peroxide under UV irradiation or in the presence of titanium tetrachloride (equations 56 and 57). Reduction of bromobenzene with sodium bis(methoxyethoxy)aluminum hydride (Red-Al, Vitride) at 100-115 C gives benzene in 53% yield (Table 4). ... 

Naphthyl phenyl sulfide is desulfurized to naphthalene on refluxing with lithium aluminum hydride and titanium tetrachloride, and 1-naphthyl ethyl sulfide and 1-naphthyl isopropyl sulfide are converted to naphthalene on treatment with ethanethiol and anhydrous aluminum chloride (equation 83). ... 

The polymerization of cyclopentadiene (5) was investigated in bulk and in solution with lithium aluminum hydride-titanium tetrachloride and lithium aluminum tetraoctyl-titanium tetrachloride catalyst systems. The polymerizations were carried out in nitrogen atmosphere using highly purified—i.e., freshly distilled— reactants. 

The reductive ring opening of 330a with sodium cyanoborohydride/titanium tetrachloride in acetonitrile occurs with no ester reduction whatsoever to provide 421 in 83% yield. Subsequent conversion to the tosylate followed by reduction with lithium borohydride/lithium triethylborohydride affords in 61% yield the crystalline diol 422. Lithium aluminum hydride or sodium borohydride reduction of the tosylate of 421 fails to produce clean reductions to 422. Epoxide ring closure of 422 is achieved with two equivalents of sodium hydroxide in methanol to fiimish in 93% yield (2 S, 3i )-2-benzyloxy-3,4-epoxybutan-l-ol (423) [140] (Scheme 94). 

Al—Ti Catalyst for cis-l,4-PoIyisoprene. Of the many catalysts that polymerize isoprene, four have attained commercial importance. One is a coordination catalyst based on an aluminum alkyl and a vanadium salt which produces /n j -l,4-polyisoprene. A second is a lithium alkyl which produces 90% i7j -l,4-polyisoprene. Very high (99%) i7j -l,4-polyisoprene is produced with coordination catalysts consisting of a combination of titanium tetrachloride, TiCl, plus a trialkyl aluminum, R Al, or a combination of TiCl with an alane (aluminum hydride derivative) (86—88). 

---