Titanium chloride tetraisopropoxide

A remarkable process was reported by Mori that forms aniline from dinitrogen (Equation (26)).106 Titanium nitrogen fixation complexes were generated from reactions of titanium tetrachloride or tetraisopropoxide, lithium metal, TMS chloride, and dinitrogen. These complexes generated a mixture of aryl and diarylamines in yields as high as 80% when treated with aryl halide and a palladium catalyst containing DPPF ... 

By using a stoichiometric amount of the chiral titanium reagent prepared by mixing chiral diol, Titanium IV) Chloride, and titanium tetraisopropoxide, the asymmetric [2 + 2] cycloaddition reaction of 1,4-benzoquinones and styrenes gives the corresponding cyclobutane derivatives with high optical purity. These rearrange to 2,3-dihydrobenzofuran derivatives on mild acid treatment (eq 13). ... 

Methoxymethyl vinyl ketone undergoes titanium(lV) chloride/titanium tetraisopropoxide catalyzed cycloaddition to either stereoisomer of 1-phenylpropene to give a mixture of the two cyclobutanes which could be equilibrated to the rrans.rrans-isomer with carbonate42. 

A new method for nitrogen fixation involved the treatment of titanium tetraisopropoxide with lithium metal and trimethylsilyl chloride in the presence of a nitrogen atmosphere to give either a titanium-nitrogen complex and/or N(TMS)3 9 (proposed structures) <04BCJ1655>. This reagent was utilized to prepare pyrrole, indoles, and other nitrogen heterocycles. For example, treatment of preformed 9 with enol triflate 8 led to fused pyrrole 10. 

Sharpless epoxidation of allyl alcohols (Sharpless, 1985, 1988 Pfenninger, 1986 Rossiter, 1985 Woodard et al., 1991 Finn and Sharpless, 1991 Corey, I990a,b), an example of which is included in Table 9.6, is perhaps the most recent and one of the most remarkable applications of asymmetric catalysis. The reaction is normally performed at low temperatures (-30 to 0°C) in methylene chloride with a titanium complex consisting of a chiral component [diethyl tartrate (DET) or diisopropyl tartrate (DIPT)] and a titanium salt (titanium tetraisopropoxide) as the catalyst. The beauty of the synthesis is that both enantiomers of the tartrate are available so that either form of the product can be prepared in more than 90% ee. 

Phosphonium ylide, generated from allyl triphenylphosphonium chloride, is capable of addition to 1-nitronaphthalene or 5-nitro-8-methoxyquinoline in the presence of DBU and titanium tetraisopropoxide to form unstable A -hydroxyindole derivative, which is transformed by action of ethyl bromoacetate into benzo- or pyridoindoles (Scheme 80) [200]. 

Titanium tetraisopropoxide s. under TiCl Trimethylsilyl chloride s. under CpjZrHCl and SnClj... 

TBDMSCl as Cl Source. TBDMSCl was used as a source of chloride ion in the Lewis acid-assisted opening of an epoxide. The epoxide was treated with TBDMSCl and triethylamine followed by titanium tetraisopropoxide and additional TBDMSCl to give the trans chloride as the major product in 67% yield (eq 10). 

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