Aryls titanium

The synthesis and reactivity of cr-bonded alkyl (see Alkyl Complexes) and aryl titanium(IV) complexes has been extensively reviewed by Bottrill et alP... 

Table 2 Carbonyl Addition Reactions of Various Alkyl- and Aryl-titanium(IV) Nucleophiles ... 

Ti( 72-propene)(OPr1)2 reacts with the two unsymmetrical acetylenes But02C-G=C-C6H13 and HC=C-G6H13 to give a dialkoxo-titanacyclopentadiene derivative (Scheme 99) which upon treatment with ethynyl tolyl sulfone produces a new single aryl-titanium compound.194... 

Transesterification between hydroxyl-esters, carboxy-esters, or two ester groups is one of the most important polyesterification technique used for preparing various aliphatic, aliphatic-aromatic or aromatic polyesters (also known as arylates). Titanium alkoxides are very efficient catalysts for transesterification polymerizations, however in some cases it can cause undesirable discoloration to the resulting polymer [15]. A representative example is the synthesis of a polyester based on dimethyl terephthalate using titanium isopropoxide [16] (Fig. 2.3). 

Therefore, methyltitanium compounds and neopentyltitanium compounds not having a -carbon atom are relatively stable as alkyltitanium compounds. The phenyl and other aryl titanium compounds are relatively stable. As described above, titanium compounds having cyclopentadienyl groups are stable and have a high melting point. Cp2TiCl2 forms a 7r-coordination distorted tetrahedral structure [30]. 

The preparations of a variety of other alkyl and aryl titanium complexes are outlined in Figure 56. All these alkyl and aryl titanium comiplexes are... 

Fig. 56. Preparation and reactions of some alkyl and aryl titanium complexes. X represents halogen or hydrocarbon ligands as indicated...

The highly regio- and diastereoselective addition of an alkyl and an arylthio group to an olefinic double bond ( carbosulfenylation ) is achieved with arenesulfenyl chlorides and alkyl-chloro-titanium(IV) species (Reetz reagent, from R2Zn/TiCU 5 1 M. T. Reetz, 1987, 1989), Use of the more bulky 2,4,6-triisopropylbenzenesulfenyl chloride improves the yield of the highly versatile alkyl aryl sulfide products. 

The carbonylation of aryl halides under mild conditions in the presence of CsF afford.s the acid fluoride 490 in good yields. Unlike acyl chlorides, acyl fluorides are inert toward Pd(0) catalyst[345]. Benzenesulfonyl chloride (491) undergoes desulfonylation-carbonylation to give the benzoate 492 in the presence of titanium tetralkoxide at 160 °C[346]. 

This can be circumvented by choosing alkyl groups with no P H, eg, methyl, neopentyl, trimethylsilylmethyl, phenyl and other aryl groups, and benzyl. The linear transition state for -elimination can also be made stericaHy impossible. The most successful technique for stabilization combines both principles. The pentahaptocyclopentadienyl ring anion (Cp) has six TT-electrons available to share with titanium. Biscyclopentadienyltitanium dichloride... 

Colona and coworkers oxidized a variety of alkyl aryl and heterocyclic sulfides to the sulfoxides using t-butyl hydroperoxide and a catalytic amount of a complex (97) derived from a transition metal and the imines of L-amino acids. Of the metals (M = TiO, Mo02, VO, Cu, Co, Fe), titanium gave the highest e.e. (21%), but molybdenum was the most efficient catalyst. The sulfoxides were accompanied by considerable sulfone125. 

High ee values have also been obtained with organometallics," including organotitanium compounds (methyl, aryl, allylic) in which an optically active ligand is coordinated to the titanium," allylic boron compounds, and organozinc compounds. 

For preparative purposes, titanium metal can be used in place of sodium or lithium in liquid ammonia for both the vinyl phosphate231 and aryl phosphate232 cleavages. The titanium metal is generated in situ from TiCl3 by reduction with potassium metal in tetrahydrofuran. 

Beller and coworkers [312] have recently published a very useful domino reaction using a Ti-based Lewis acid as catalyst to prepare indoles. The new procedure consists of a titanium-catalyzed amination of a chloroalkylalkyne to give an aryl hydra-... 

Seebach and coworkers have developed enantioselective conjugate additions of primary dialkylzinc reagents to 2-aryl- and 2-heteroaryl-nitroalkenes mediated by titanium-TADDO-Lates (Eq. 4.90). x a TADDOLs and their derivatives are excellent chiral auxiliaries.9611... 

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