Petasis reagent

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Not to be confused with Petasis reaction.
Petasis reagent
Structural formula of the Petasis reagent
Ball-and-stick model of the Petasis reagent
Names
IUPAC name
Bis(η5-cyclopentadienyl)dimethyltitanium
Other names
Dimethyltitanocene
Identifiers
1271-66-5 YesY
Jmol-3D images Image
Properties
C12H16Ti
Molar mass 208.13 g/mol
Hazards
Main hazards Irritant, incompatible with water and oxidizing agents
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

The Petasis reagent is an organotitanium compound with the formula Cp2Ti(CH3)2.[1] It is an orange-colored solid.

Preparation and use[edit]

It prepared by the salt metathesis reaction of methylmagnesium chloride or methyllithium[2] with titanocene dichloride:[3]

Cp2TiCl2 + 2 CH3MgCl → Cp2Ti(CH3)2 + 2 MgCl2

The compound is used for transforming carbonyl groups to terminal alkenes. In terms of reactivity, it resembles the Tebbe reagent and Wittig reaction. Unlike the Wittig reaction, the Petasis reagent can react with a wide range of carbonyls, including aldehydes, ketones and esters.[4] The Petasis reagent is also more air stable than the Tebbe reagent, and can be isolated as a pure solid, or used directly as a solution in toluene-THF.

The reaction mechanism is very similar to that of the Tebbe reagent. The active olefinating reagent, Cp2TiCH2, is generated in situ upon heating the solution of Petasis reagent in toluene or THF to 60 °C. With the organic carbonyl, this titanium carbene forms a four membered oxatitanacyclobutane that releases the terminal alkene.[5]

See also[edit]

References[edit]

  1. ^ N. A. Petasis and E. I. Bzowej (1990). "Titanium-mediated carbonyl olefinations. 1. Methylenations of carbonyl compounds with dimethyltitanocene". J. Am. Chem. Soc. 112 (17): 6392–6394. doi:10.1021/ja00173a035. 
  2. ^ Claus, K.; Bestian, H. (1962). "Über die Einwirkung von Wasserstoff auf einige metallorganische Verbindungen und Komplexe". Justus Liebigs Ann. Chem. 654: 8. doi:10.1002/jlac.19626540103. 
  3. ^ Payack, J. F.; Hughes, D. L.; Cai, D.; Cottrell, I. F.; Verhoeven, T. R. (2002). "Dimethyltitanocene". Org. Synth. 79: 19. 
  4. ^ Hartley, R. C.; Li, J.; Main, C. A.; McKiernan, G. J. (2007). "Titanium carbenoid reagents for converting carbonyl groups into alkenes". Tetrahedron 63 (23): 4825–4864. doi:10.1016/j.tet.2007.03.015. 
  5. ^ Meurer, Eduardo Cesar; Santos, Leonardo Silva; Pilli, Ronaldo Aloise; Eberlin, Marcos N. (2003). "Probing the Mechanism of the Petasis Olefination Reaction by Atmospheric Pressure Chemical Ionization Mass and Tandem Mass Spectrometry". Organic Letters 5 (9): 1391–4. doi:10.1021/ol027439b. PMID 12713281.