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Organic and Biomolecular Chemistry
Volumn 8, Issue 15, 2010, Pages 3444-3450
Radical allylations by reaction of azides with allylindium dichloride
Author keywords

[No Author keywords available]
Indexed keywords

ALLYLATION REACTIONS; ALLYLATIONS; ANALOGOUS REACTIONS; CHAIN REACTION; ELECTROPHILIC CARBON; GOOD YIELD; H MIGRATION; METAL BONDS; NITROGEN HETEROCYCLES; THEORETICAL CALCULATIONS;
EID: 77954650727     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/c001848a     Document Type: Article
Times cited : (7)
References (107)
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    • Radicals in Organic Synthesis, vol. 1 and 2, ed., P. Renaud, and, M. P. Sibi,, Wiley-VCH, Weinheim, 2001
    • (2001) Radicals in Organic Synthesis, Vol. 1 and 2, Ed.
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    • Although toxicity data on organoindium compounds are not available to a great extent, it is worth admitting that the few accessible information suggest there could be no significant improvement, as far as toxicity is strictly concerned, by substituting tin with indium. The greenness of organoindium compounds is rather a matter of workupand purification of reaction products. Employment of dichloroindium hydride or allylindium dichloride results in inorganic, water-soluble metal byproducts that can be easily, quantitatively removed from the reaction crude: this prevents noteworthy contamination of organic reaction products, hence overcoming the main problems associated with use of organotin reagents
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  • 73
    • 33845282675 scopus 로고
    • 2 radical was very unlikely, due to the broadening effect of the Indium quadrupole moment; hence all efforts were devoted to detection of the radical counterpart, i.e. the allyl radical. The optimal temperature of -13 °C was determined after several attempts at various temperatures
    • M. Yamaji Y. Hama S. Arai M. Oshino Inorg. Chem. 1987 26 4375
    • (1987) Inorg. Chem. , vol.26 , pp. 4375
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  • 74
    • 84989095400 scopus 로고
    • Photolytic self-decomposition of those azides does not occur to a significant extent under our experimental conditions. Normal alkyl or aryl azides (the latter even with electron-withdrawing substituents) were recovered completely unreacted upon treatment after many hours with allylindium dichloride under photolytic initiation; in this case, the radical chain reaction is probably hindered by the low electrophilicity of the intermediate indiumaminyl radicals, which, by analogy with other metal-substituted congeners, are actually supposed to be slightly nucleophilic (see ref. 6e,f, 7, and 8i)
    • J. K. Kochi P. J. Krusic J. Am. Chem. Soc 1968 90 7157
    • (1968) J. Am. Chem. Soc , vol.90 , pp. 7157
    • Kochi, J.K.1    Krusic, P.J.2
  • 76
    • 4243108187 scopus 로고    scopus 로고
    • It is worth noting that, whereas the reactions of azides 1 and 2 were not substantially affected by the solvent (THF or benzene), those of azides 3 and 4 showed a dramatic effect: in THF the starting azides were recovered substantially unchanged after prolonged photolysis, whereas, after 3 h in benzene solution, we observed complete conversion into the products reported in Scheme 3. This impressive difference could be due to either the hydrogen donor features of THF, which may quench the initial aminyl radicals in a chain-breaking reaction, or the complexing properties of this solvent, which could alter the real structure of the allylindium reagent and thence its reactivity towards these particular azides
    • P. Panchaud L. Chabaud Y. Landais C. Ollivier P. Renaud S. Zigmantas Chem. Eur. J. 2004 10 3606
    • (2004) Chem. Eur. J. , vol.10 , pp. 3606
    • Panchaud, P.1    Chabaud, L.2    Landais, Y.3    Ollivier, C.4    Renaud, P.5    Zigmantas, S.6
  • 84
    • 0027082198 scopus 로고
    • Although addition of tin radicals to azides is normally carried out at 80 °C or above, it seems very unlikely that at r.t. this reaction would slow down enough to inhibit the whole reaction. For a few examples of reactions performed below 80 °C, see:
    • H. Rolland P. Potin J. -P. Majoral G. Bertrand Tetrahedron Lett. 1992 33 8095
    • (1992) Tetrahedron Lett. , vol.33 , pp. 8095
    • Rolland, H.1    Potin, P.2    M, J.-P.3    Bertrand, G.4
  • 99
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    • a values obtained by HF calculations are unmistakably far away from reality but, like in the case of the BDEs reported above, it is worth pointing out that they confirm the relative trend, giving differences in enthalpies and activation barriers strictly comparable with those obtained by DFT, hence providing further support to the mechanistic discussion
    • Y.-r. Luo, Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press, Boca Raton, 2003, p. 297
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    • L, Y.-R.1
  • 103
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    • Benzene is very toxic and carcinogenic (R45) and every possible precaution must be taken when handling this solvent. However, our reactions can be effectively carried out by replacing benzene with other aromatic hydrocarbons such as tert-butylbenzene or toluene
    • N. Khoukhi M. Vaultier R. Carrié Tetrahedron 1987 43 1811
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    • Khoukhi, N.1    Vaultier, M.2    Carrié, R.3

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.