Barbier reaction

Barbier reaction

The Barbier reaction is an organic reaction between an alkyl halide and a carbonyl group as an electrophilic substrate in the presence of aluminium, zinc, indium, tin or its salts. The reaction product is a secondary or tertiary alcohol. The reaction is similar to the Grignard reaction but the crucial difference is that the Barbier reaction is a one-pot synthesis whereas a Grignard reagent is prepared separately before addition of the carbonyl compound. [cite journal | author = Barbier, P. | journal = Compt. Rend. | year = 1899 | volume = 128 | pages = 110] Barbier reactions are nucleophilic addition reactions that take place with relatively inexpensive and water insensitive metals or metal compounds in contrast to Grignard reagents or organolithium reagents. For this reason it is possible in many cases to run the reaction in water which makes the procedure part of green chemistry. The Barbier reaction is named after Victor Grignard’s teacher Philippe Barbier.

Examples of Barbier reactions are the reaction of propargylic bromide with butanal with zinc metal in water: [cite journal | title = Zn Mediated Regioselective Barbier Reaction of Propargylic Bromides in THF/aq. NH4Cl Solution | author = Artur Jõgi and Uno Mäeorg | journal = Molecules | year = 2001 | volume = 6 | pages = 964–968 | url = http://www.mdpi.org/molecules/papers/61200964.pdf ]


With a substituted alkyne instead of a terminal alkyne the allene product is favoured

the intramolecular Barbier reaction with samarium(II) iodide: [cite journal | title = Preparation of oxo-substituted α-chloro ethers and their reaction with samarium diiodide | author = Tore Skjæret and Tore Benneche | journal = Arkivoc | pages = KU–242A | year = 2001 | url = http://www.arkat-usa.org/ark/journal/2001/I10_Undheim/242/242.asp ]

the reaction of an allyl bromide with formaldehyde in THF with indium powder: [OrgSynth | title = Methyl 3-(hydroxymethyl)-4-methyl-2-methylenepentanoate | author = George D. Bennett and Leo A. Paquette | collvol = 10 | collvolpages = 77 | prep = v77p0107]


The Barbier reaction is accompanied by an allylic rearrangement to a terminal alkene

or another allyl bromide in a reaction with benzaldehyde and zinc powder in water: [cite journal | title = Use of Cyclic Allylic Bromides in the Zinc–Mediated Aqueous Barbier–Grignard Reaction | author = Gary W. Breton, John H. Shugart, Christine A. Hughey, Brian P. Conrad, Suzanne M. Perala | journal = Molecules | year = 2001 | volume = 6 | pages = 655–662 | url = http://www.mdpi.org/molecules/papers/60800655.pdf]


The observed diastereoselectivity for this reaction is erythro : threo = 83 : 17

Related reactions: Grignard reaction, Nozaki-Hiyama-Kishi reaction

External links

* Barbier reaction @ University of Connecticut [http://orgchem.chem.uconn.edu/namereact/barbier.html Website]

References


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