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Synthesis 2001(9): 1321-1326
DOI: 10.1055/s-2001-15220
DOI: 10.1055/s-2001-15220
PAPER
© Georg Thieme Verlag Stuttgart · New York
Highly Regioselective and Stereoselective Radical Addition of p-TsBr to Substituted Terminal Allenes and Their Nucleophilic Substitutions: Synthesis of α,β-Unsaturated Sulfones
Further Information
Received
8 February 2001
Publication Date:
24 September 2004 (online)
Publication History
Publication Date:
24 September 2004 (online)
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Abstract
Regioselective and stereoselective radical addition of p-TsBr to substituted allenes in the presence of a catalytic amount of AIBN afforded tosyl-substituted primary (E)-allylic bromides as the sole products. The nucleophilic substitution of the resulting allylic bromides to give substituted α,β-unsaturated sulfone derivatives is described.
Keywords
allenes - radical reactions - sulfones - nucleophilic substitutions
- 1 Review:
Bertrand MP. Org. Prep. Proced. Int. 1994, 26: 257 - 2
Simpkins NS. In Sulphones in Organic Sythesis Pergamon Press; Oxford: 1993. -
3a Hatem et al. reported the radical cyclization of the allylallenes:
Gueddari FE.Grimaldi JR.Hatem JM. Tetrahedron Lett. 1995, 36: 6685 -
3b Caddick et al. also reported the cyclization of 1,5-diynes with p-TsBr and AIBN:
Caddick S.Shering CL.Wadman SN. Chem. Commun. 1997, 171 -
3c Bertrand et al. investigated the photo-induced radical addition of p-TsBr to the tethered 1,6-dienes to form heterocycles:
DeRiggi I.Surzur J.-M.Bertrand MP. Tetrahedron 1988, 44: 7119 -
3d
Cristol S.Davies DI. J. Org. Chem. 1964, 29: 1282 -
3e
Nouguier R.Lesueur C.DeRiggi E.Bertrand MP.Virgili A. Tetrahedron Lett. 1990, 31: 3541 -
3f Wang et al. reported the chemoselective photochemical addition of TsBr to acrylamides and cyclization to form lactams:
Wang C.Russel GA. J. Org. Chem. 1999, 64: 2346 -
4a
Byrd LR.Caserio MC. J. Org. Chem. 1972, 37: 3881 -
4b
Truce WE.Heuring DL.Wolf GC. J. Org. Chem. 1974, 39: 238 -
4c
Truce WE.Heuring DL. J. Org. Chem. 1974, 39: 245 - 5
Simpkins NS. Tetrahedron 1990, 46: 6951 - 6
Poshkus AC.Herrweh JE.Magnotta FA. J. Org. Chem. 1963, 28: 2766 - 8 It is reported by Bäckvall that the kinetical allylic malonate rearranges to its thermodynamically more stable regioisomer, see:
Nilsson YIM.Andersson PG.Bäckvall JE. J. Am. Chem. Soc. 1993, 115: 6609
References
The E stereochemistry of 3a, 3b, 3d, and 3e was confirmed by 1H NMR NOE experiments (Figure).
Figure