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2
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Scheme 4. Reagents and conditions: (a) 2 equiv. TsSePh, 2–3
5
equiv. AIBN, CHCl , reflux, 15 h; (b) NaOMe, 20% MeOH in
3
THF, reflux, 18 h (see Table 2).
6
7
. For further examples of intermolecular radical reactions
involving solid supported substrates, see: (a) Caddick,
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Table 2. Details of reactions highlighted in Schemes 1 and
4
Reaction
Yield (from 8) (%)
cis:trans
1
1
1
1
1
3
74
72
66
69
68
8:1
3:1
ꢀ[3:3]:[1:1]
ꢀ[1:1]:[1:1]
1:1
0a14a
0b14b
0c14c
0d14d
(
d) Miyabe, H.; Tanaka, H.; Naito, T. Tetrahedron
Lett. 1999, 40, 8387–8390; (e) Yim, A. M.; Vidal, Y.;
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4535–4538.
8
. For examples of thiyl radical induced cyclisation reac-
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hedron Lett. 2000, 41, 9345–9349; (b) Harrowven, D.
C.; Lucas, M. C.; Howes, P. D. Tetrahedron 2001, 57,
the 2°-alkyl radical intermediate is trapped with SePh.
As this step proceeds in an indiscriminate manner,
complex product mixtures comprising four diastereoiso-
mers were given in each case. These products could be
partially separated by HPLC, allowing us to show that
cyclisation of 10b favoured the cis-1,2-substitution pat-
tern (Scheme 4, Table 2).
7
91–804; (c) Harrowven, D. C.; Hannam, J. C. Tetra-
hedron 1999, 55, 9341–9346; (d) Harrowven, D. C.;
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4
443–4444; (e) Naito, T.; Honda, Y.; Miyata, O.;
Ninomiya, I. J. Chem. Soc., Perkin Trans. 1 1995, 19–
6; (e) Ogawa, A.; Tanaka, H.; Yokoyama, H.;
2
In conclusion, we have shown that solid supported
Obayashi, R.; Yokoyama, K.; Sonoda, N. J. Org.
Chem. 1992, 57, 111–115; (f) Miyata, O.; Shinada, T.;
Ninomiya, I.; Naito, T. Synthesis 1990, 1123–1125; (g)
Ichinose, Y.; Wakamatsu, K.; Nozaki, K.; Birbaum, J.-
L.; Oshima, K.; Utimoto, K. Chem. Lett. 1987, 1647–
1
,6-dienes may be transformed into cyclopentanes
through the action of either thiyl or sulfonyl radical
intermediates. Good yields are attained using PS-Wang
as the support and stereochemical outcomes mirror
15
those of the analogous solution phase reactions.
1650; (h) Kuehne, M. E.; Damon, R. E. J. Org. Chem.
1977, 42, 1825–1832; (i) Oswald, A. A.; Griesbaum K.
In The Chemistry of Organic Sulfur Compound; Kha-
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Acknowledgements
1
966; Vol. 2, Chapter 9, pp. 233–256.
The authors thank David Pallin for his interest in this
work and Rh oˆ ne-Poulenc Rorer and EPSRC for the
provision of a CASE studentship (to P.J.M.).
9
1
. Chuang, C.-P. Synth. Commun. 1992, 22, 3151–3158.
0. Semmelhack, M. F.; Foos, J. S.; Katz, S. J. Am. Chem.
Soc. 1973, 95, 7325–7336.
1
1. Bennet, W. D.; Christensen, J. W.; Hamaker, L. K.;
Peterson, M. L.; Rhodes, M. R.; Saneii, H. H. Hand-
book of Combinatorial and Solid Phase Organic Chem-
istry; Advanced ChemTech Inc.: Louisville, 1998.
References
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. For recent overviews of radical cyclisation reactions,
see: (a) Giese, B.; Kopping, B.; G o¨ bel, T.; Dickhaut, J.;
Thoma, G.; Kulicke, K. J.; Trach, F. Org. React. 1996,
12. AIBN was added hourly from the commencement of
each reaction in nine equal portions.