Organozinc compound
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Organozinc compounds in organic chemistry contain carbon to zinc chemical bonds. Organozinc chemistry is the science of organozinc compounds describing their physical properties, synthesis and reactions [1] [2] [3].
The first organozinc ever prepared, diethylzinc by Edward Frankland in 1849, was also the first ever compound with a metal to carbon sigma bond. Many organozinc compounds are pyrophoric and therefore difficult to handle. Organozinc compounds in general are sensitive to oxidation, dissolve in a wide variety of solvents where protic solvents cause decomposition. In many reactions they are prepared in situ, not isolated and reacted further. All reactions require a protective gas (nitrogen or argon) blanket.
The three main classes of organozincs are: organozinc halides R-Zn-X with X a halogen atom, diorganozincs R-Zn-R with R an alkyl or aryl group and lithium zincates or magnesium zincates M+R3Zn- with M lithium or magnesium.
The carbon zinc bond is polarized towards carbon due to the differences in electronegativity (carbon:2.55 and zinc: 1.65). Diorganozincs are always monomeric, the organozinc halides form aggregates through halogen bridges very much like Grignard reagents and also like Grignards they display a Schlenk equilibrium.
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[edit] Synthesis
Several general methods exist for the generation of organozinc compounds.
- Oxidative addition. The original diethylzinc synthesis by Frankland was an oxidative addition of iodoethane to zinc metal with hydrogen gas as a "protective" blanket. The reactivity of zinc metal is increased in so-called Rieke zinc obtained by reduction of zinc chloride by potassium metal.
- Halogen zinc exchange. Two main halogen zinc exchange reactions are iodine zinc exchange and boron zinc exchange. The first step in the second procedure is hydroboration of an alkene:
- Transmetalation. In a typical transmetalation, diphenylmercury reacts with zinc metal to diphenylzinc and metallic mercury in diethyl ether. Reaction time: two weeks. This reaction is driven by the formation of the organic compound with the most electropositive element.
- Organozinc compounds can be obtained directly from zinc metal [4] [5]:
- In this method zinc is activated by the action of 1,2-dibromoethane and trimethylsilyl chloride. A key ingredient is lithium chloride which quickly forms a soluble adduct with the organozinc compound thus removing it from the metal surface.
[edit] Reactions
In many of their reactions organozincs appear as intermediates.
- The Barbier reaction (1899) is the zinc equivalent of the magnesium Grignard reaction and actually the older and the more tolerant of the two. In presence of just about any water the formation of the organomagnesium halide will fail whereas the Barbier reaction can even take place in water. On the downside organozincs are much less nucleophilic than Grignards. Among the Group 12 elements zinc is the most reactive.
- The Reformatskii reaction converts α-halo-esters and aldehydes to β-hydroxy-esters also through an intermediate organozinc halide.
- In the Simmons-Smith reaction the carbenoid (iodomethyl)zinc iodide reacts with alkens to cyclopropanes
- Reactions of zinc metal acetylides
- Addition reaction of organozinc compounds to carbonyl compounds. Commercially available diorganozinc compounds are dimethylzinc, diethylzinc and diphenylzinc. These reagents are expensive and difficult to handle. In one study [6] [7] the active organozinc compound is obtained from much cheaper organobromine precursors:
- The Negishi coupling is an important reaction for the formation of new carbon carbon bonds between unsaturated carbon atoms in alkenes, arenes and alkynes. The catalysts are nickel and palladium. A key step is the catalytic cycle is a transmetalation in which a zinc halide exchanges its organic substituent for another halogen with the palladium (nickel) metal center.
[edit] See also
- Other chemistries of carbon with Group 12 elements
- Other chemistries of carbon with Period 4 elements
- organotitanium compounds
- organovanadium compounds
- organochromium compounds
- organomanganese compounds
- organoiron compounds
- organocobalt compounds
- organonickel compounds
- organocopper compounds
- organogallium compounds
- organogermanium compounds
- organoarsenic compounds
- organoselenium compounds.
[edit] References
- ^ The Chemistry of Organozinc Compounds (Patai Series: The Chemistry of Functional Groups), (Eds. Z. Rappoport and I. Marek), John Wiley & Sons: Chichester, UK, 2006, ISBN 0-470-09337-4.
- ^ Organozinc reagents - A Practical Approach, (Eds. P. Knochel and P. Jones), Oxford Medical Publications, Oxford, 1999, ISBN 0-19-850121-8.
- ^ Synthetic Methods of Organometallic and Inorganic Chemistry Vol 5, Copper, Silver, Gold, Zinc, Cadmium, and Mercury, W.A. Herrmann Ed., ISBN 3-13-103061-5
- ^ Efficient Synthesis of Functionalized Organozinc Compounds by the Direct Insertion of Zinc into Organic Iodides and Bromides Arkady Krasovskiy, Vladimir Malakhov, Andrei Gavryushin, Paul Knochel Angewandte Chemie International Edition Volume 45, Issue 36 , Pages 6040 - 6044 2006 DOI:10.1002/anie.200601450
- ^ In this example the arylzinc iodide continues to react with allyl bromide in a nucleophilic displacement
- ^ From Aryl Bromides to Enantioenriched Benzylic Alcohols in a Single Flask: Catalytic Asymmetric Arylation of Aldehydes , J.G. Kim and P.J. Walsh, Angewandte Chemie International Edition, Volume 45, Issue 25 , Pages 4175-4178, 2006, DOI:10.1002/anie.200600741
- ^ In this one-pot reaction bromobenzene is converted to phenyllithium by reaction with 4 equivalents of n-butyllithium, then transmetalation with zinc chloride forms diphenylzinc which continues to react in an asymmetric reaction first with the MIB ligand and then with 2-naphthylaldehyde to the alcohol. In this reaction formation of diphenylzinc is accompanied by that of lithium chloride, which unchecked, catalyses the reaction without MIB involvement to the racemic alcohol. The salt is effectively removed by chelation with tetraethylethylene diamine (TEEDA) resulting in an enantiomeric excess of 92%.
