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Volumn 63, Issue 15, 1998, Pages 5076-5079

Highly Regioselective Palladium-Catalyzed Internal Arylation of Allyltrimethylsilane with Aryl Triflates

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EID: 0001584519     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980249n     Document Type: Article
Times cited : (69)

References (77)
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    • Allylsilanes similar to 2-aryl-3-(trimethylsilyl)-1-propenes have been used for the synthesis of carbacephames and HIV-1 protease inhibitors; see: (d) Oumoch, S.; Rousseau, G. Bioorg. Med. Chem. Lett. 1994, 4, 2841.
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    • For the preparation of 3d by arylation of 1,3-bis(trimethylsilyl)-1-propene, see ref 4. For a selection of other methods for the preparation of 3, see the following. Via organocerium: (a) Narayan, B. A.; Bunnelle, W. H. Tetrahedron Lett. 1987, 28, 6261.
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    • Some recent examples where the β-effect has been utilized in organic synthesis: (h) Thorimbert, S.; Malacria, M. Tetrahedron Lett. 1996, 37, 8483.
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    • DPPF = 1, 1′-bis(diphenylphosphino)ferrocene, DPPP = 1,3-bis(diphenylphosphino)propane. For a discussion of the properties of DPPF, see: Gan, K. S.; Hor, T. S. A. In Ferrocenes; Togni, A., Hayashi, T., Eds.; VCH: Weinheim, 1995; p 3.
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    • Initial screening experiments revealed that acetonitrile leads to a smaller extent of desilylation and better regioselectivities than other solvents (DMF, NMP, dioxane, and DMSO) for this particular reaction, for a recent discussion of the palladium-mediated mechanism of desilylation, see: LaPointe, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906. See also ref 6h.
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    • note
    • As regards the desilylation process, a higher degree of desilylation takes place as the temperature rises but the desilylation is brought about in the product-forming stage of the reaction and does not change markedly thereafter, suggesting that the desilylation is palladium-mediated. See also refs 4 and 6h.
  • 53
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    • The microwave technique lends its efficiency mainly from the fact that a polar, homogeneous reaction mixture will be heated faster under microwave irradiation than under thermal heating. Apart from this, the boiling point elevation due to pressure in a closed Pyrex tube allows higher temperatures than are ordinarily feasable. (a) Hájek, M. Collect. Czech. Chem. Commun. 1997, 62, 347.
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    • Acetonitrile is known to be of sufficient polarity for efficient heating in microwave fields; see: (b) Stone-Elander, S.; Elander, N. Appl. Radiat. Isot. 1991, 42, 885.
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    • Kingston, H. M., Jassie, L. B., Eds.; American Chemical Society: Washington, DC
    • For a theoretical discussion of microwave irradiation, see: (c) Neas, E. D.; Collins, M. J. Introduction to Microwave Sample Preparation; Kingston, H. M., Jassie, L. B., Eds.; American Chemical Society: Washington, DC, 1988; p 7.
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    • We have previously reported on the application of microwave irradiation in palladium-catalyzed synthesis. (a) Larhed, M.; Lindeberg, G.; Hallberg, A.; Tetrahedron Lett. 1996, 37, 8219.
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    • A similar β-stabilized cation complex has been suggested by Hosomi et al.; see ref 5j
    • A similar β-stabilized cation complex has been suggested by Hosomi et al.; see ref 5j.
  • 66
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    • According to GC/MS analyses, four compounds were formed. Hydrogenation, delivering two compounds, allowed determination of the regioselectivity ratio. See Phenylation of 4-Methyl-1-pentene in the Experimental Section
    • According to GC/MS analyses, four compounds were formed. Hydrogenation, delivering two compounds, allowed determination of the regioselectivity ratio. See Phenylation of 4-Methyl-1-pentene in the Experimental Section.
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    • The fact that minute amounts of the unbranched 3-aryl-1-propene, possibly derived from a concomitant Stille reaction, was observed by NMR made an accurate determination of the regiocontrol difficult. The heavier elements in the group (Sn and Pb) have been reported to be more easily displaced than the lighter elements (Si and Ge). For a discussion of this phenomenon, see ref 6c. Internally arylated allylstannane compounds are unstable; see: Desponds, O.; Schlosser, M. J. Organomet. Chem. 1991, 93.
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    • Acetonitrile from recently opened bottles resulted in better regioselectivities than acetonitrile from old bottles
    • Acetonitrile from recently opened bottles resulted in better regioselectivities than acetonitrile from old bottles.
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    • For an excellent review on organic triflates, see: Ritter, K. Synthesis 1993, 735.
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    • The following paper contains more detailed spectroscopic data of a partly deuterated analogue: (b) Tseng, C. C.; Paisley, S. D.; Goering, H. L. J. Org. Chem. 1986, 51, 2884.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.