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Microwave-Assisted Meyer–Schuster Rearrangement of Propargylic Alcohols Catalyzed by the Oxovanadate Complex [V(O)Cl(OEt)2]
Article first published online: 6 OCT 2011
DOI: 10.1002/cctc.201100239
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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How to Cite
Antiñolo, A., Carrillo-Hermosilla, F., Cadierno, V., García-Álvarez, J. and Otero, A. (2012), Microwave-Assisted Meyer–Schuster Rearrangement of Propargylic Alcohols Catalyzed by the Oxovanadate Complex [V(O)Cl(OEt)2]. ChemCatChem, 4: 123–128. doi: 10.1002/cctc.201100239
Publication History
- Issue published online: 27 DEC 2011
- Article first published online: 6 OCT 2011
- Manuscript Received: 18 JUL 2011
Funded by
- Ministerio de Ciencia e Innovación (MICINN). Grant Numbers: CSD2007-00006, CTQ2008-00506/BQU, CTQ2010-14796/BQU, CTQ2009-09214/BQU
- Junta de Comunidades de Castilla-La Mancha. Grant Number: PCI08–0032
- MICINN
- European Social Fund
- 1See, for example:
- 1ain Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon Press, Oxford, 1991, pp. 1–67;
- 1bin Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon Press, Oxford, 1991, pp. 69–137;
- 1cin Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon Press, Oxford, 1991, pp. 139–168;
- 1din Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon Press, Oxford, 1991, pp. 169–198;
- 1e
- 1fin Science of Synthesis, Vol. 26 (Ed.: J. Cossy), Thieme Verlag, Stuttgart, 2004, pp. 1045–1121;
- 1g, in Science of Synthesis, Vol. 25 (Eds.: R. Brückner, E. Schaumann), Thieme Verlag, Stuttgart, 2006, pp. 733–777.
- 2, , , in Organic Chemistry, Oxford University Press, Oxford, 2001.
- 3For review articles highlighting the concept of atom economy, see:
- 3a
- 3b, Angew. Chem. 1995, 107, 285–307;Angew. Chem. Int. Ed. Engl. 1995, 34, 259–281;Direct Link:Direct Link:
- 3c
- 3d
- 3e, , , Angew. Chem. 2005, 117, 6788–6825;Angew. Chem. Int. Ed. 2005, 44, 6630–6666;Direct Link:Direct Link:
- 3f
- 4
- 5For early reviews, see:
- 5a
- 5b
- 6
- 7For reviews on metal-catalyzed Meyer–Schuster rearrangements, see:
- 7a
- 7b
- 8A protocol for the selective Meyer–Schuster rearrangement of propargylic alcohols using boronic acids as catalysts under mild conditions has been recently disclosed: , , , Chem. Sci. 2011, 2, 1305–1310.
- 9
- 9a
- 9b
- 10
- 10a, , , Adv. Synth. Catal. 2011, 353, 585–594;Direct Link:
- 10b
- 10c
- 11, , , , , Chem. Eur. J. 2010, 16, 9555–9562.Direct Link:
- 12
- 12a
- 12b
- 13
- 13a
- 13b
- 13c
- 14
- 15
- 16Application of metal-catalyzed Meyer–Schuster rearrangements to the synthesis of (S)-α-ionone and prostaglandins has also been described recently:
- 16a, , , , , Chem. Eur. J. 2009, 15, 3940–3944;Direct Link:
- 16b
- 16c
- 17The mechanism of the isomerization of 2-methyl-3-butyn-2-ol into 3-methyl-2-butenal, catalyzed by an oxotitanium complex, has been previously investigated by synthesizing several compounds that model the postulated metal-oxo-propargyloxo intermediate. , , , , Polyhedron 2000, 19, 1693–1698.
- 18The basis of this reaction is a [3,3]-sigmatropic transposition of the metal-oxo intermediate. Similar reactions are also known for allylic alcohols using molybdenum, vanadium, or rhenium catalysts.
- 18a
- 18b
- 18c
- 18d
- 18e, , , , Angew. Chem. 1997, 109, 1011–1013;Angew. Chem. Int. Ed. Engl. 1997, 36, 976–978;Direct Link:Direct Link:
- 18f
- 18g, , , , , Angew. Chem. 2006, 118, 2654–2657; Angew. Chem. Int. Ed. 2006, 45, 2592–2595; Angew. Chem. Int. Ed. 2006, 45, 2592–2595;Direct Link:
- 18h
- 18i
- 18j
- 19
- 19aVariants involving the direct addition of the propargylic OH group across the M
O bond have also been proposed; in this case, a hydroxo–propargyloxo species [M(OH)(OCR2R3C
CR1)] is involved in the [3,3]-sigmatropic rearrangement: see reference [16a]; - 19bIntroduction of a Lewis acid cocatalyst able to coordinate to the C
C bond of propargylic alcohol is also known to favor the key [3,3]-sigmatropic rearrangement step: , , , , Org. Lett. 2008, 10, 1867–1870. - 20For a recent review, see: , , , , , Coord. Chem. Rev. 2011, 255, 2345–2357.
- 21
- 21a, , Fr. Pat. FR1554805, 1969;
- 21b, , U. S. Pat. US3920751, 1975;
- 21c
- 21d
- 21e
- 21f
- 21g
- 21h, , Ger. Pat. DE2657335, 1977;
- 21i, in Flavors and Fragrances: A World Perspective, (Eds.: B. M. Lawrence, B. D. Mookherjee, B. J. Willis), Elsevier Science Publishers, Amsterdam, 1988;
- 21j
- 21k
- 21l
- 21msee also reference [15].
- 22Meyer–Schuster isomerization of ethoxyalkynyl carbinols catalyzed by the vanadium(IV) derivative [V(O)(acac)2] has also been described: see reference[12].
- 23
- 24
- 25See, for example:
- 25aMicrowaves in Organic Synthesis (Ed.: A. Loupy), Wiley-VCH, Weinheim, 2006;
- 25b, , in Practical Microwave Synthesis for Organic Chemists, Wiley-VCH, Weinheim, 2009;
- 25cMicrowave Heating as a Tool for Sustainable Chemistry (Ed.: N. E. Leadbeater), CRC Press, Boca Raton, 2011.
- 26The use of lower temperatures and/or catalyst loadings slowed down the reaction considerably; as an example, by using 1 mol % of complex 2 under MW irradiation (300 W) at 80 °C, 3,3-diphenylpropenal was formed in only 80 % GC yield after 1 h.
- 27This total Meyer–Schuster-versus-Rupe selectivity was also observed previously for the related vanadium(V) catalyst [V(O)(OSiPh3)3]: see reference [21g].
- 28Such an E selectivity with secondary alkynols has been rarely observed using oxo complexes as catalysts: see reference [16a]. However, several examples of stereoselective non-oxo catalytic systems are known: see, for example, references [16b,c] and
- 28a
- 28b
- 28c
- 29For a recent review article and a book on the chemistry of these species, see:
- 29a
- 29b, , in Chemistry of α,β-Unsaturated Trifluoromethyl Ketones, Nova Science Publishers, New York, 2007.
- 30These substrates can be easily accessed by the addition of CF3C
CLi, generated in situ from commercially available 2-bromo-3,3,3-trifluoropropene and lithium diisopropylamide, to the corresponding carbonyl compound. See, for example: - 30a
- 30b
- 30c
- 31Redox-type isomerizations, that is, isomerizations not involving a 1,3-shift of the hydroxyl moiety, of CF3-containing secondary propargylic alcohols into enones were described recently: , , J. Org. Chem. 2011, 76, 1957–1960.
- 32Primary propargylic alcohols have been proven to be very difficult substrates for the Meyer–Schuster reaction. Only one successful methodology involving the combined use of cis-[MoO2(acac)2], [AuCl(PPh3)], and AgOTf has been described to date in the literature: see reference [19b].
- 33
- 34
- 34a
- 34b

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