Tebbe's reagent

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Tebbe's reagent
Structure of Tebbe's reagent
Ball-and-stick model of Tebbe's reagent
Names
IUPAC name
μ-Chloro[di(cyclopenta-2,4-dien-1-yl)]dimethyl(μ-methylene)titaniumaluminum
Other names
Tebbe reagent
Identifiers
3D model (
JSmol
)
ChemSpider
ECHA InfoCard
 100.157.162 Edit this at Wikidata
UNII
  • InChI=1S/2C5H5.2CH3.CH2.Al.Cl.Ti/c2*1-2-4-5-3-1;;;;;;/h2*1-5H;2*1H3;1H2;;;/q2*-1;;;;-1;+1;+2 ☒N
    Key: FHPQZKBPAZOMGO-UHFFFAOYSA-N ☒N
  • InChI=1/2C5H5.2CH3.CH2.Al.Cl.Ti/c2*1-2-4-5-3-1;;;;;;/h2*1-5H;2*1H3;1H2;;;/q2*-1;;;;-1;+1;+2/r2C5H5.C3H8AlClTi/c2*1-2-4-5-3-1;1-4(2)3-6-5-4/h2*1-5H;3H2,1-2H3/q2*-1;+2
    Key: FHPQZKBPAZOMGO-SBUAZLESAR
  • C[Al-]1(C[Ti+2][Cl+]1)C.[cH-]1cccc1.[cH-]1cccc1
Properties
C13H18AlClTi
Molar mass 284.60 g/mol
Solubility in other solvents toluene, benzene, dichloromethane,
THF (low temperatures only)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Tebbe's reagent is the

Fred Tebbe at DuPont Central Research
.

Tebbe's reagent contains two tetrahedral metal centers linked by a pair of bridging ligands. The titanium has two cyclopentadienyl ([C
5H
5]−
, or Cp) rings and aluminium has two methyl groups. The titanium and aluminium atoms are linked together by both a methylene bridge (-CH2-) and a chloride atom in a nearly square-planar (Ti–CH2–Al–Cl) geometry.[2] The Tebbe reagent was the first reported compound where a methylene bridge connects a transition metal (Ti) and a main group metal (Al).[3]

Preparation

The Tebbe reagent is synthesized from titanocene dichloride and trimethylaluminium in toluene solution.[3][4]

Cp2TiCl2 + 2 Al(CH3)3 → CH4 + Cp2TiCH2AlCl(CH3)2 + Al(CH3)2Cl

After about 3 days, the product is obtained after recrystallization to remove Al(CH3)2Cl.[3] Although syntheses using the isolated Tebbe reagent give a cleaner product, successful procedures using the reagent "in situ" have been reported.[5][6] Instead of isolating the Tebbe reagent, the solution is merely cooled in an ice bath or dry ice bath before adding the starting material.

An alternative but less convenient synthesis entails the use of

dimethyltitanocene (Petasis reagent):[7]

Cp2Ti(CH3)2 + Al(CH3)2Cl → Cp2TiCH2AlCl(CH3)2 + CH4

One drawback to this method, aside from requiring Cp2Ti(CH3)2, is the difficulty of separating product from unreacted starting reagent.

Reaction mechanism

Tebbe's reagent itself does not react with carbonyl compounds, but must first be treated with a mild

Schrock carbene
.

Tebbe reagent equilib

Also analogous to the Wittig reagent, the reactivity appears to be driven by the high oxophilicity of Ti(IV). The Schrock carbene (1) reacts with carbonyl compounds (2) to give a postulated oxatitanacyclobutane intermediate (3). This cyclic intermediate has never been directly isolated, presumably because it breaks down immediately to the produce the desired alkene (5).

The reaction mechanism of methylidenation using the Tebbe reagent

Scope

The Tebbe reagent is used in organic synthesis for carbonyl methylidenation.[8] [9][10] This conversion can also be effected using the Wittig reaction, although the Tebbe reagent is more efficient especially for sterically encumbered carbonyls. Furthermore, the Tebbe reagent is less basic than the Wittig reagent and does not give the β-elimination products.

Methylidenation reactions also occur for

lactones and amides
. The Tebbe reagent converts esters and lactones to enol ethers and amides to enamines. In compounds containing both ketone and ester groups, the ketone selectively reacts in the presence of one equivalent of the Tebbe reagent.

The Tebbe reagent methylidenates carbonyls without racemizing a chiral α carbon. For this reason, the Tebbe reagent has found applications in reactions of sugars where maintenance of stereochemistry can be critical.[11]

The Tebbe reagent reacts with

acid chlorides
to form titanium enolates by replacing Cl−.

Modifications

It is possible to modify Tebbe's reagent through the use of different ligands. This can alter the reactivity of the complex, allowing for a broader range of reactions. For example, cyclopropanation can be achieved using a chlorinated analogue.[12]

Amide cyclopropanation

See also

Related organotitanium reagents and reactions

Related methylidenation reactions

References

  1. doi:10.1021/ja00479a061
    .
  2. doi:10.1021/om401108b
    .
  3. ^ a b c Herrmann, W.A., "The Methylene Bridge" Advances in Organometallic Chemistry 1982, 20, 195–197.
  4. ^ Straus, D. A., "μ-Chlorobis(cyclopentadienyl)(dimethylaluminium)-μ-methylenetitanium": Encyclopedia of Reagents for Organic Synthesis. John Wiley, London, 2000.
  5. doi:10.15227/orgsyn.069.0072
    .
  6. doi:10.1021/jo00213a040
    .
  7. ^ Payack, J. F.; Hughes, D. L.; Cai, D.; Cottrell, I. F.; Verhoeven, T. R. (2004). "Dimethyltitanocene". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 10, p. 355.
  8. doi:10.1016/j.tet.2007.03.015
    .
  9. ^ Pine, S. H. Org. React. 1993, 43, 1. (Review)
  10. ^ Beadham, I.; Micklefield, J. Curr. Org. Synth. 2005, 2, 231–250. (Review)
  11. doi:10.1021/ja00042a010.{{cite journal}}: CS1 maint: multiple names: authors list (link
    )
  12. Org. Lett.; 2006; 8(11) pp 2265 – 2267; Abstract
  13. doi:10.15227/orgsyn.065.0081
    ..
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