Radical addition to, isonitriles: A route to polyfunctionalized alkenes through a novel three-component radical cascade reaction

Journal of Organic Chemistry

Volumn 65, Issue 9, 2000, Pages 2763-2772

  Leardini, Rino ^a   Nanni, Daniele ^a   Zanardi, Giuseppe ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AROMATIC COMPOUND; DISULFIDE; ISONITRILE DERIVATIVE; RADICAL;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; CHEMICAL STRUCTURE; GEOMETRY; ISOMERISM; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0034607923     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991871y     Document Type: Article

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63. This is consistent with the disulfide dissociation equilibrium, which is shifted towards the reagent by lowering the dilution. Synthetically useful reactions with photolytically generated sulfanyl radicals are therefore usually carried out at high dilutions.
64. Leardini, R.; Nanni, D.; Zanardi, G. Eur. J. Org. Chem., 2000, 707. Analogous compounds were always obtained, generally in small amounts, in all of the subsequent reactions (see the Experimental Section).
65. At least one fate was in principle conceivable-and expected-for imidoyl radical 10, i.e., six-membered cyclization onto the S-phenyl ring. In fact, it has been reported that imidoyls can give 1,6-ring closure onto aromatic rings, at least under oxidative conditions (see ref 4b). Under the present conditions this process is probably slow and it cannot compete with the α-fragmentation reaction giving back the isonitrile and the vinyl radical. Another possibility was the trap of radical 10 by another sulfanyl radical to give an N-bis(arylthio)methylene derivative. These products were actually obtained in low to moderate yields by reacting isonitriles and disulfides in the absence of alkynes or hydrogen donors, but they were never observed in the present study.
66. Although data on the reversibility of radical addition to isonitriles-as well as homolytic fragmentations providing vinyl radicals-are not available in the literature, we found evidence that, at least with particularly stable radicals, this reaction is likely to be reversible (see ref 4j). Further support to a reversible radical addition to isonitriles will be reported below.
67. All of these compounds have been commonly observed in the reactions between sulfanyl radicals and phenylacetylene (see ref 6a,b). However, since we did not use thiols as a source of sulfanyl radicals, we were quite astonished to obtain the hydrogen-abstraction product 4a in significant amounts. In our reaction, one of the possible hydrogen-atom sources could be tentatively identified as the cyclohexadienyl radicals involved in the formation of compound 5a.
68. For trapping of radicals by nitro groups resulting in oxygen-transfer reactions from the nitro moiety to the radical center, see, for example: Topiwala, U. P.; Luszniak, M. C.; Whiting, D. A. J. Chem. Soc., Perkin Trans, 1 1998, 1185.
69. It is worth noting that the literature has reported several examples of both sulfanyl radical addition to isonitriles (see refs 2a,d,g and 41) and imidoyl radical addition to alkynes (see ref 4a,c,h and: Dan-oh, Y.; Malta, H.; Uemura, J.; Watanabe, H.; Uneyama, K. Bull. Chem. Soc. Jpn. 1995, 68, 1497). Therefore, one could envisage an alternative reaction pathway including sulfanyl radical addition to 3 followed by reaction of the resulting α-thio-imidoyl radical with 2 to give a vinyl radical. Cyclization of the latter intermediate onto the isonitrile aryl ring could lead to a quinoline derivative. Nevertheless, this kind of product was never observed under any experimental conditions.
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71. A large excess of isonitrile is essential to trap the vinyl radical efficiently. When we used 5 mmol of 14, the yield dropped to 15%.
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74. For the use of vinyl sulfides in organic synthesis, see: Cookson, R. C.; Parson, P. J. J. Chem. Soc., Chem. Commun. 1976, 990. Ager, D. J. J. Chem. Soc., Perkin Trans. 1 1983, 1131. Oshima, K.; Shimoji, K.; Takahashi, H.; Yamamoto, H.; Nozaki, H. J. Am. Chem. Soc. 1973, 95, 2694.
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82. In all of the reactions described in this paper, the alkene having the alkyne-derived group and the sulfanyl moiety on the same side of the C-C double bond is more stable than the other isomer. This was suggested by the silica-catalyzed isomerization observed during column chromatography and it was definitively proved by photolyses of each of the (supposed) less stable isomers in the presence of the corresponding disulfide. After 24 h under these conditions, they gave almost complete conversion to the alkene with the opposite configuration, due to reversible sulfanyl radical addition to the C-C double bond. See: (a) Kice, J. L. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York, 1973; Vol. II, pp 720-724. (b) Oswald, A. A.; Griesbaum, K.; Hudson, B. E., Jr.; Bregman, J. M. J. Am. Chem. Soc. 1964, 86, 2877. (c) Kampmeier, J. A.; Chen, G. J. Am. Chem. Soc. 1965, 87, 2608. (d) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1967, 32, 3837. It is worth noting that the most stable configuration is named E for the alkene obtained from phenylacetylene (and 1-hexyne, see below) but Z for that arising from trimethylsilylacetylene, due to the presence of the silicon atom instead of a carbon.
83. In all of the reactions described in this paper, the alkene having the alkyne-derived group and the sulfanyl moiety on the same side of the C-C double bond is more stable than the other isomer. This was suggested by the silica-catalyzed isomerization observed during column chromatography and it was definitively proved by photolyses of each of the (supposed) less stable isomers in the presence of the corresponding disulfide. After 24 h under these conditions, they gave almost complete conversion to the alkene with the opposite configuration, due to reversible sulfanyl radical addition to the C-C double bond. See: (a) Kice, J. L. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York, 1973; Vol. II, pp 720-724. (b) Oswald, A. A.; Griesbaum, K.; Hudson, B. E., Jr.; Bregman, J. M. J. Am. Chem. Soc. 1964, 86, 2877. (c) Kampmeier, J. A.; Chen, G. J. Am. Chem. Soc. 1965, 87, 2608. (d) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1967, 32, 3837. It is worth noting that the most stable configuration is named E for the alkene obtained from phenylacetylene (and 1-hexyne, see below) but Z for that arising from trimethylsilylacetylene, due to the presence of the silicon atom instead of a carbon.
84. In all of the reactions described in this paper, the alkene having the alkyne-derived group and the sulfanyl moiety on the same side of the C-C double bond is more stable than the other isomer. This was suggested by the silica-catalyzed isomerization observed during column chromatography and it was definitively proved by photolyses of each of the (supposed) less stable isomers in the presence of the corresponding disulfide. After 24 h under these conditions, they gave almost complete conversion to the alkene with the opposite configuration, due to reversible sulfanyl radical addition to the C-C double bond. See: (a) Kice, J. L. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York, 1973; Vol. II, pp 720-724. (b) Oswald, A. A.; Griesbaum, K.; Hudson, B. E., Jr.; Bregman, J. M. J. Am. Chem. Soc. 1964, 86, 2877. (c) Kampmeier, J. A.; Chen, G. J. Am. Chem. Soc. 1965, 87, 2608. (d) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1967, 32, 3837. It is worth noting that the most stable configuration is named E for the alkene obtained from phenylacetylene (and 1-hexyne, see below) but Z for that arising from trimethylsilylacetylene, due to the presence of the silicon atom instead of a carbon.
85. In all of the reactions described in this paper, the alkene having the alkyne-derived group and the sulfanyl moiety on the same side of the C-C double bond is more stable than the other isomer. This was suggested by the silica-catalyzed isomerization observed during column chromatography and it was definitively proved by photolyses of each of the (supposed) less stable isomers in the presence of the corresponding disulfide. After 24 h under these conditions, they gave almost complete conversion to the alkene with the opposite configuration, due to reversible sulfanyl radical addition to the C-C double bond. See: (a) Kice, J. L. In Free Radicals; Kochi, J. K., Ed.; Wiley: New York, 1973; Vol. II, pp 720-724. (b) Oswald, A. A.; Griesbaum, K.; Hudson, B. E., Jr.; Bregman, J. M. J. Am. Chem. Soc. 1964, 86, 2877. (c) Kampmeier, J. A.; Chen, G. J. Am. Chem. Soc. 1965, 87, 2608. (d) Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1967, 32, 3837. It is worth noting that the most stable configuration is named E for the alkene obtained from phenylacetylene (and 1-hexyne, see below) but Z for that arising from trimethylsilylacetylene, due to the presence of the silicon atom instead of a carbon.
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