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Volumn 349, Issue 3, 2007, Pages 382-394

A novel propargylation/cycloisomerization tandem process catalyzed by a ruthenium(II)/trifluoroacetic acid system: One-pot entry to fully substituted furans from readily available secondary propargylic alcohols and 1,3-dicarbonyl compounds

Author keywords

1,3 dicarbonyl compounds; Cycloisomerization; Furans; Propargylic alcohols; Propargylic substitution reactions; Ruthenium

Indexed keywords


EID: 34547168331     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200600366     Document Type: Article
Times cited : (83)

References (90)
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    • We note that, although monosubstituted alkynols HC≡ CC(OH)HR (R, aryl group) also undergo the Meyer-Schuster isomerization into enals in the presence of complex 1 (see ref.[4, attempts to promote its one-pot coupling with acetone resulted in the formation of the corresponding (EE)-dienones · RCH=CHCH=C(H)C(= O)Me (C) in remarkably low yieldssee ref.[3, The monitoring of these reactions by GC showed, in addition to the complete consumption of the starting propargylic alcohol, that some uncharacterized by-products are also formed pointing out the existence of competitive processes in solution involving probably furan ring formation
    • [3]). The monitoring of these reactions by GC showed, in addition to the complete consumption of the starting propargylic alcohol, that some uncharacterized by-products are also formed pointing out the existence of competitive processes in solution involving probably furan ring formation.
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    • 2].
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    • 4 (10 mol%), has been recently reported: Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. Hidai, S. Uemura, J. Org. Chem. 2004, 69, 3408-3412.
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    • Formation of tri- and tetrasubstituted furans from secondary propargylic alcohols and enolizable ketones, in the presence of catalytic amounts of [Cp*RuCl(μ2-SMe)2RuCp*Cl, 10 mol, NH4BF4 (20 mol, and PtCl2 (20 mol, has been reported. This process involves also the initial formation of a γ-ketoalkyne, via Ru-catalyzed propargylic substitution of the alkynol with the ketone, which undergoes a Pt-catalyzed Markovnikov hydration of the alkyne moiety to give a 1,4-diketone. Subsequent cyclization of this diketone, also catalyzed by Pt, generates the final furans. We note that (i) no 1,3-dicarbonyl compounds were used as substrates in this catalytic reaction, and (ii) the process is only operative with terminal alkynols HC≡CC(OH)-HAr Ar, aryl group, Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. D. Milton, M. Hidai, S. Uemura, Angew. Chem. Int. Ed. 2003, 42, 2681-2684
    • 2 (20 mol%), has been reported. This process involves also the initial formation of a γ-ketoalkyne, via Ru-catalyzed propargylic substitution of the alkynol with the ketone, which undergoes a Pt-catalyzed Markovnikov hydration of the alkyne moiety to give a 1,4-diketone. Subsequent cyclization of this diketone, also catalyzed by Pt, generates the final furans. We note that (i) no 1,3-dicarbonyl compounds were used as substrates in this catalytic reaction, and (ii) the process is only operative with terminal alkynols HC≡CC(OH)-HAr (Ar = aryl group): Y. Nishibayashi, M. Yoshikawa, Y. Inada, M. D. Milton, M. Hidai, S. Uemura, Angew. Chem. Int. Ed. 2003, 42, 2681-2684.
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    • 7CCCO)].
    • 7CCCO)].
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    • The Boc group is known to be a versatile and widely used protecting group for carboxylic acids. Several methods have been reported for its removal, most of them involving the use of Brønsted (HCl, H2SO4, HNO3 or CF3CO2H) or Lewis (I2, TiCl4, ZnBr2, CeCl3, SiO2 or silyl triflates) acids. Representative references are the following: a) J. S. Yadav, E. Balanarsaiah, S. Raghavendra, M. Satyanarayana, Tetrahedron Lett. 2006, 47, 4921-4924;
    • 2 or silyl triflates) acids. Representative references are the following: a) J. S. Yadav, E. Balanarsaiah, S. Raghavendra, M. Satyanarayana, Tetrahedron Lett. 2006, 47, 4921-4924;
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    • The carboxylic acid 12a could not be detected by GC/ MS pointing out that its decarboxylation is a highly favoured process.
    • The carboxylic acid 12a could not be detected by GC/ MS pointing out that its decarboxylation is a highly favoured process.
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    • Transition metal-catalyzed decarboxylation of carboxylic acids is a well-documented process. Representative examples can be found in: a) S. Matsubara, Y. Yokota, K. Oshima, Org. Lett. 2004, 6, 2071-2073;
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    • 3 which undergoes the addition of the nucleophile (in our case the enolic form of the 1,3-dicarbonyl compound acts as a carbon-centered nucleophile): R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodriguez, Eur. J. Org. Chem. 2006, 1383-1386;
    • 3 which undergoes the addition of the nucleophile (in our case the enolic form of the 1,3-dicarbonyl compound acts as a carbon-centered nucleophile): R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodriguez, Eur. J. Org. Chem. 2006, 1383-1386;
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    • it should be also noted that very recently two general and highly efficient procedures for the propargylic substitution of alkynols catalyzed by the Lewis acids BiCl3 and FeCl3 have been reported: Z.-P. Zhan, W.-Z. Yang, R.-F. Yang, X-L. Yu, J.-P. Li, H.-J. Liu, Chem. Commun. 2006, 3352-3354;
    • 3 have been reported: Z.-P. Zhan, W.-Z. Yang, R.-F. Yang, X-L. Yu, J.-P. Li, H.-J. Liu, Chem. Commun. 2006, 3352-3354;
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    • Although complex 1 is known to be an active catalyst in propargylic substitution processes of alkynols with alcohols (see ref.[4a, it is not active at all when carboncentered nucleophiles, such as enolizable ketones, are used as substrates see ref.[3
    • [3]).
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    • In accord with previous results, the treatment of 2a with methyl acetoacetate and complex 1 (5 mol, at 75°C and in the absence of CF 3CO2H, results in the exclusive formation of enal (E)-RHC=CHCHO (R, 1-naphthyl) as the result of the Meyer-Schuster isomerization of the alkynol see ref.[4b
    • [4b]).
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    • 2 can be cycloisomerized into furans in the presence of copper(I) salts. All these reactions are believed to proceed through the intermediate formation of allenyl isomers that undergo metal-mediated cyclization: a) H. Sheng, S. Lin, Y. Huang, Synthesis 1987, 1022-1023;
    • 2 can be cycloisomerized into furans in the presence of copper(I) salts. All these reactions are believed to proceed through the intermediate formation of allenyl isomers that undergo metal-mediated cyclization: a) H. Sheng, S. Lin, Y. Huang, Synthesis 1987, 1022-1023;
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    • For reviews on this topic see: a
    • For reviews on this topic see: a) M. I. Bruce, Chem. Rev. 1991, 91, 197-257;
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    • It should be noted that other ruthenium(II) sources, such as [RuCl 2(PPh3)3, RuCl2(DMSO) 4, RuCl(μ-Cl)(η6-p-cymene)}2, RuCl(η5-C5H5)(PPh3) 2, RuCl(η5-C9H7)(PPh 3)2] and [Ru(η3-C3H 4Me)2(COD, were also found to be operative in this furan-ring formation reaction. Nevertheless, their efficiency is by far lower than that shown by complex 1. Thus, using the coupling of alkynol 2c with ethyl acetoacetate as a model reaction, 2c, ethyl acetoacetate, CF 3CO2H, Ru] ratio, 20:200:10:1, the best results were obtained using [RuCl2(DMSO)4] and [Ru(η3-2- C3H4Me)2(COD, which give furan 8c in 60, and 64, yield GC determined, respectively, after
    • 2(COD)] which give furan 8c in 60 % and 64 % yield (GC determined), respectively, after 8 h (to be compared with entry 4 in Table 2).


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