- Barton-McCombie deoxygenation
The Barton-McCombie deoxygenation is an
organic reaction in which anhydroxy functional group in anorganic compound is replaced by ahydride to give an alkyl group [cite journal
author = Barton, D. H. R.; McCombie, S. W.
journal = J. Chem. Soc., Perkin Trans. 1
title = A new method for the deoxygenation of secondary alcohols
year = 1975
volume = 16
pages = 1574–1585
doi = 10.1039/P19750001574] [cite journal
author = Crich, D.; Quintero, L.
journal =Chem. Rev.
title = Radical chemistry associated with the thiocarbonyl group
year = 1989
volume = 89
pages = 1413–1432
doi = 10.1021/cr00097a001] . It is named for the British chemists SirDerek Harold Richard Barton (1918–1998) and Stuart W. McCombie.This deoxygenation reaction is a
radical substitution . In the relatedBarton decarboxylation the reactant is acarboxylic acid .Mechanism
The
reaction mechanism consists of a catalytic radical initiation step and a propagation step. [Forbes, J. E.; Zard, S. Z. "Tetrahedron Lett. " 1989, "30", 4367.] Thealcohol (1) is first converted into axanthate (2). The other reactant tributyltin hydride 3 is decomposed byAIBN 8 into a tributyltin radical 4. The tributyltin radical abstracts the xanthate group from 2 leaving analkyl radical 5 and tributyltin xanthate (7). Thesulfur tin bond in this compound is very stable and provides the driving force for this reaction. The alkyl radical in turn abstracts a hydrogen atom from a new molecule of tributyltin hydride generating the desired deoxygenated product (6) and a new radical species ready for propagation.Variations
Alternative hydride sources
Main disadvantage of this reaction is the use of the tin hydride which is toxic, expensive and difficult to remove from the reaction mixture. One alternative is the use of tributyltin anhydride as the radical source and poly(methylhydridesiloxane) (PMHS) as the
hydride source [α-D-Ribo-hexofuranose, 3-deoxy-1,2:5,6-bis-O-(1-methylethylidene). Tormo, J.; Fu, G. C. "Org. Syn. ", Coll. Vol. 10, p.240 (2004); Vol. 78, p.239 (2002). ( [http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=v78p0239 Article] )] . Phenyl chlorothionoformate used as the starting material ultimately generatescarbonyl sulfide .Trialkyl boranes
An even more convenient hydrogen donor is provided by trialkylborane-water complexes ["Deoxygenation of Alcohols Employing Water as the Hydrogen Atom Source" David A. Spiegel, Kenneth B. Wiberg, Laura N. Schacherer, Matthew R. Medeiros, and John L. Wood "
J. Am. Chem. Soc. " 2005, "127", 12513-12515. (DOI|10.1021/ja052185l)] such as trimethylborane contaminated with small amounts of water.In this
catalytic cycle the reaction is initiated by air oxidation of the trialkylborane 3 by air to the methyl radical 4. This radical reacts with the xanthate 2 to S-methyl-S-methyl dithiocarbonate 7 and the radical intermediate 5. The CH3B.H2O complex 3 provides a hydrogen for recombining with this radical to the alkane 6 leaving behind diethyl borinic acid and a new methyl radical.It is found by theoretical calculations that that a O-H
homolysis reaction in the borane-water complex is endothermic with an energy similar to that of the homolysis reaction in tributyltin hydride but much lower than the homolysis reaction of pure water.cope
A variation of this reaction was used as one of the steps in the
total synthesis ofazadirachtin ["Synthesis of Azadirachtin: A Long but Successful Journey" Gemma E. Veitch, Edith Beckmann, Brenda J. Burke, Alistair Boyer, Sarah L. Maslen, andSteven V. Ley Angew. Chem. Int. Ed. 2007, DOI|DOI: 10.1002/anie.200703027] ::
In another variation the reagent is the
imidazole 1,1'-thiocarbonyldiimidazole (TCDI), for example in the total synthesis of pallescensin B. ["The first total synthesis of (±)-pallescensin B" Wen-Cheng Liu and Chun-Chen LiaoChem. Commun. , 1999, 117–118 117 [http://rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=a808714h&JournalCode=CC Article] ] . TCDI is especially good to primary alcohols because there is no resonance stabilization of the xanthate because the nitrogen lonepair is involved in the aromatic sextet.:
The reaction also applies to S-alkylxanthates. With
triethylborane as a novel metal-free reagent, the required hydrogen atoms are abstracted from protic solvents, the reactor wall or even (in strictly anhydrous conditions) the borane itself. ["Part 2. Mechanistic aspects of the reduction of S-alkyl-thionocarbonates in the presence of triethylborane and air" Allais F, Boivin J, Nguyen VBeilstein Journal of Organic Chemistry , 2007 3:45 ( 12 December 2007 ) doi|10.1186/1860-5397-3-46]References
External links
* [http://www.organic-chemistry.org/namedreactions/barton-mccombie-reaction.shtm Barton-McCombie @ organic-chemistry.org]
*Chemical & Engineering News [http://pubs.acs.org/cen/news/83/i35/8335notw1.html article on alkylborane reaction]
Wikimedia Foundation. 2010.