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Volumn 64, Issue 11, 1999, Pages 4095-4101

Allyl- and benzylindium reagents. Carboindation of carbon-carbon and carbon-nitrogen triple bonds

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; ALLYLINDIUM DERIVATIVE; UNCLASSIFIED DRUG;

EID: 0033612233     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo990160x     Document Type: Article
Times cited : (91)

References (51)
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    • 2O and aqueous/dry THF have been studied: (a) Paquette, L. A.; Mitzel, T. M. Tetrahedron Lett. 1995, 36, 6863. (b) Paquette, L. A.; Mitzel, T. M. J. Am. Chem. Soc. 1996, 118, 1931. (c) Paquette, L. A.; Mitzel, T. M. J. Org. Chem. 1996, 61, 8799.
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    • 2O and aqueous/dry THF have been studied: (a) Paquette, L. A.; Mitzel, T. M. Tetrahedron Lett. 1995, 36, 6863. (b) Paquette, L. A.; Mitzel, T. M. J. Am. Chem. Soc. 1996, 118, 1931. (c) Paquette, L. A.; Mitzel, T. M. J. Org. Chem. 1996, 61, 8799.
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    • 0039874886 scopus 로고    scopus 로고
    • 2O and aqueous/dry THF have been studied: (a) Paquette, L. A.; Mitzel, T. M. Tetrahedron Lett. 1995, 36, 6863. (b) Paquette, L. A.; Mitzel, T. M. J. Am. Chem. Soc. 1996, 118, 1931. (c) Paquette, L. A.; Mitzel, T. M. J. Org. Chem. 1996, 61, 8799.
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    • note
    • 2) group acts as a ligand of the In complex (ref 4). Accordingly, if the addition of the indium reagents to acetylenes proceeds in quantitative yield, 0.5 equiv of the reagents are needed for 1 equiv of acetylenes. Normally, we used 0.6 equiv of the reagents toward 1 equiv of acetylenes.
  • 30
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    • note
    • The allylation of TMS-substituted alkynes with allylzinc bromide gives the same regioselectivity as the present allylindation (ref 3d).
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    • A double-zincation intermediate was proposed in the allylzincation of terminal alkynes: Frangin, Y.; Gaudemar, M. J. Organomet. Chem. 1977, 142, 9. See also: Knochel, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, p 883.
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  • 32
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    • Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford
    • A double-zincation intermediate was proposed in the allylzincation of terminal alkynes: Frangin, Y.; Gaudemar, M. J. Organomet. Chem. 1977, 142, 9. See also: Knochel, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, p 883.
    • (1991) Comprehensive Organic Synthesis , vol.4 , pp. 883
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  • 33
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    • The stereoselectivity of the addition of aluminum hydride to alkynes was precisely studied. According to the study, the transcarbometalation product is favored thermodynamically under high-temperature reaction conditions: Eisch, J. J.; Rhee, S.-G. J. Am. Chem. Soc. 1975, 97, 4673. See also ref 2d, p 280.
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    • note
    • Negishi et al. reported the palladium-catalyzed coupling reaction of vinylic bromides and alkenylalane, which was prepared in situ from alkynes and alkylaluminum hydride (ref 2c).
  • 35
    • 0345102311 scopus 로고    scopus 로고
    • note
    • In the three-component coupling reaction, a fair amount of byproducts (mono- and dibenzylation products 18a and 22, respectively) were formed along with 21.
  • 36
    • 0344671429 scopus 로고    scopus 로고
    • note
    • 1H NMR and GC-MS showed that 22 was obtained as a single stereoisomer. The Z-conformation were assigned by the analogy from the result of 18a-d (Scheme 2).
  • 37
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    • note
    • 2-Pd-(II)X′ species, which would undergo the transmetalation reaction with the vinylindium 20 to give the vinylpalladium intermediate. Reductive elimination would give the three-component coupling product along with the Pd(0) catalyst.
  • 38
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    • note
    • 4
  • 39
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    • note
    • The protonation would take place at the workup stage: normally, an acidic silica gel column was used (see Experimental Section). On the other hand, when the reaction was quenched with diluted HCl, the desired allylation - enamination product was not obtained.


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