Solid-phase intermolecular radical reactions 1. Sulfonyl radical addition to isolated alkenes and alkynes

Tetrahedron Letters

Volumn 40, Issue 40, 1999, Pages 7285-7288

  Caddick, Stephen ^a,b   Hamza, Daniel ^a,b   Wadman, Sjoerd N ^a,b  

^a UNIVERSITY OF SUSSEX   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

Author keywords

Alkene; Alkyne; Radicals; Solid phase reactions; Toluenesulfonyl radicals

Indexed keywords

ALKENE; ALKYNE; RADICAL;

ARTICLE; CHEMICAL MODIFICATION; SOLID;

EID: 0033214241     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01525-7     Document Type: Article

References (14)

1. W. B. Motherwell and D. Crich, Free Radical Chain Reactions in Organic Synthesis, Academic Press, London, 1991; B. Giese, Radicals in Organic Synthesis: Formation of Carbon Carbon Bonds, Pergamon Press, Oxford, 1986; D. P. Curran, Synthesis, 1988, 419 & 489.
2. W. B. Motherwell and D. Crich, Free Radical Chain Reactions in Organic Synthesis, Academic Press, London, 1991; B. Giese, Radicals in Organic Synthesis: Formation of Carbon Carbon Bonds, Pergamon Press, Oxford, 1986; D. P. Curran, Synthesis, 1988, 419 & 489.
3. W. B. Motherwell and D. Crich, Free Radical Chain Reactions in Organic Synthesis, Academic Press, London, 1991; B. Giese, Radicals in Organic Synthesis: Formation of Carbon Carbon Bonds, Pergamon Press, Oxford, 1986; D. P. Curran, Synthesis, 1988, 419 & 489.
4. C. P. Jasperse, D. P. Curran, T. Fervig, Chem. Rev. 1991, 1237.
5. J. Junggebauer, W. P. Neumann, Tetrahedron, 1997, 53, 1301.
6. A. Routledge, C. Abell, S. Balasubramanian, Synlett, 1997, 61; X. H. Du; R. W. Armstrong, J. Org. Chem. 1997, 62, 5678.
7. A. Routledge, C. Abell, S. Balasubramanian, Synlett, 1997, 61; X. H. Du; R. W. Armstrong, J. Org. Chem. 1997, 62, 5678.
8. For an example of addition of solid-supported radicals to allylic stannanes see M. Sibi, S. V. Chandramouli, Tetrahedron Lett. 1997, 38, 8929. For bimolecular addition of radicals to solidsupported activated alkenes see: A-M Yim, Y. Vidal, P. Viallefont, J. Martinez, Tetrahedron Lett.1999, 40, 4535; H. Miyabe, Y. Fujishima, T. Naito, J. Org. Chem. 1999, 64, 2174; X. Zhu, A. Ganesan, J. Comb. Chem. 1999, 1, 157.
9. For an example of addition of solid-supported radicals to allylic stannanes see M. Sibi, S. V.Chandramouli, Tetrahedron Lett. 1997, 38, 8929. For bimolecular addition of radicals to solid supported activated alkenes see: A-M Yim, Y. Vidal, P. Viallefont, J. Martinez, Tetrahedron Lett. 1999, 40, 4535; H. Miyabe, Y. Fujishima, T. Naito, J. Org. Chem. 1999, 64, 2174; X. Zhu, A. Ganesan, J. Comb. Chem. 1999, 1, 157.
10. For an example of addition of solid-supported radicals to allylic stannanes see M. Sibi, S. V.Chandramouli, Tetrahedron Lett. 1997, 38, 8929. For bimolecular addition of radicals to solidsupported activated alkenes see: A-M Yim, Y. Vidal, P. Viallefont, J. Martinez, Tetrahedron Lett.1999, 40, 4535; H. Miyabe, Y. Fujishima, T. Naito, J. Org. Chem. 1999, 64, 2174; X. Zhu, A. Ganesan, J. Comb. Chem. 1999, 1, 157.
11. For an example of addition of solid-supported radicals to allylic stannanes see M. Sibi, S. V.Chandramouli, Tetrahedron Lett. 1997, 38, 8929. For bimolecular addition of radicals to solidsupported activated alkenes see: A-M Yim, Y. Vidal, P. Viallefont, J. Martinez, Tetrahedron Lett.1999, 40, 4535; H. Miyabe, Y. Fujishima, T. Naito, J. Org. Chem. 1999, 64, 2174; X. Zhu, A. Ganesan, J. Comb. Chem. 1999, 1, 157.
12. S. Caddick, C. L. Shering, S. N. Wadman, J. Chem. Soc., Chem. Commun. 1997, 171; S. Caddick, C. L. Shering, S. N. Wadman, Tetrahedron Lett. 1997, 38, 6249.
13. S. Caddick, C. L. Shering, S. N. Wadman, J. Chem. Soc., Chem. Commun. 1997, 171; S. Caddick, C. L. Shering, S. N. Wadman, Tetrahedron Lett. 1997, 38, 6249.
14. General procedure for preparation of tosyl bromide: To a stirred, aqueous solution (100ml) of sodium p-toluenesulfinate (1eq, 3g), bromine (1eq, 2.47g) was added dropwise with further stirring for 30 minutes upon complete addition. Crude TsBr was filtered and dried in vacuo (69% yield) and recrystallised from carbon tetrachloride (53% yield) m.p. 92-93° C. (Lit. 91-92° C). General procedure for addition/cleavage: p-Toluenesulfonyl bromide (6eq, 0.6mmol) and azobisisobutyronitrile (6eq, 0.6mmol) were pre-dissolved in anhydrous toluene (~1ml) and added to a resin-linked acceptor (1eq, 0.1mmol). The reaction was performed in a 2ml Reactivial™ at 65-70°C for 16-22 hours and allowed to cool to room temperature. The resin was then washed copiously with portions of DMF, DCM, THF, DMSO, acetic acid and once with 20% DIPEA/DMF*. Cleavage from resin using 95% TFA(aq) gave the product. *Prolonged washing of the alkene addition products with base can lead to trace quantities of eliminated product.