Petasis reagent

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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
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.204.841
Properties
C12H16Ti
Molar mass 208.13 g/mol
Hazards
Main hazards Irritant, incompatible with water and oxidizing agents
Except where otherwise noted, data are 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]

The Petasis reagent is prepared by the salt metathesis reaction of methylmagnesium chloride or methyllithium[2] with titanocene dichloride:[3]

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

This compound is used for the transformation of carbonyl groups to terminal alkenes. It exhibits similar reactivity to the Tebbe reagent and Wittig reaction. Unlike the Wittig reaction, the Petasis reagent can react with a wide range of aldehydes, ketones and esters.[4] The Petasis reagent is also very air stable, and is commonly used in solution with toluene or THF.

The Tebbe reagent and the Petasis reagent share a similar reaction mechanism. The active olefinating reagent, Cp2TiCH2, is generated in situ upon heating. 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 & 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". Organic Syntheses. 79: 19.CS1 maint: Multiple names: authors list (link)
  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.