Petasis reagent dimethyltitanocene

Dimethyltitanocene (213), called the Petasis reagent, can be used for alkenation of carbonyls (aldehydes, ketones, esters, thioesters and lactones). This reagent is prepared more easily than the Tebbe reagent by the reaction of titanocene dichloride with MeLi. However, this reagent may not be a carbene complex and its reaction may be explained as a nucleophilic attack of the methyl group at the carbonyl [67], Alkenylsilanes are prepared from carbonyl compounds. Tri(trimethylsilyl)titanacyclobutene (216), as a... 

A useful alternative to phosphorus ylids are the titanium reagents, such as, 71, prepared from dicyclopentadienyltitanium dichloride and trimethylaluminum. Treatment of a carbonyl compound with the titanium cyclopentadienide complex 71 Tebbe s reagent) in toluene-THF containing a small amount of pyridine " leads to the alkene. Dimethyltitanocene (Me2TiCp2), called the Petasis reagent, is a convenient and highly useful alternative to The mechanism of Petasis... 

The Petasis reagent (Me2TiCp2, dimethyltitanocene) undergoes similar olefi-nation reactions with ketones and aldehydes. The originally proposed mechanism [3] was very different from that of Tebbe olefmation. However, later experimental data seem to suggest that both Petasis and Tebbe olefmation share the same mechanism, i.e. the carbene mechanism involving a four-membered titanium oxide ring intermediate [6]. 

The Petasis reagent (Me2TiCp2, dimethyltitanocene) undergoes similar olefination reactions with ketones and aldehydes [5]. However, the mechanism is very different. 

Petasis, et al. have discovered that dimethyltitanocene is an excellent substitute for the Tebbe reagent" for the methylenation of heteroatom-substituted carbonyl compounds. ... 

---