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Li, G.; Wei, H. X.; Gao, J.; Caputo, T. D. Tetrahedron Lett. 2000, 41, 1. In this paper Li and co-workers have clearly mentioned that the electron-withdrawing group is necessary on the aromatic ring for obtaining modest yields and a better reaction rate in the titanium tetrachloride mediated Baylis-Hillman reaction between aromatic aldehydes and cyclic enones and they employed 4-nitrobenzaldehyde and 4-(trifluoromethyl)benzaldehyde as electrophiles in this reaction.
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Li, G.1
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note
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3, (of the cyclohex-2-enone moiety) are on the same side in the extended conformation].
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31
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0038270821
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note
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Detailed X-ray crystallographic data for compound 5 is available from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, U.K. (CCDC no. 184079).
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0038609708
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1H NMR data (particularly the chemical shifts of benzylic and/or olefinic protons) of Baylis-Hillman and aldol compounds obtained from cyclohex-2-enone and aromatic aldehydes were reported in the literature.
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8,11 it may not be possible to confirm the complete absence of syn-aldol product because of the possibility of the doublet (or dd in case benzylic-H couples with the OH proton) hidden in this multiplet. Because the intensity of this multiplet itself (at δ 5.42-5.52) is much lower than that of singlet at δ 5.56, the syn-aldol product, even if formed, might be in much smaller amounts in comparison with that of the Baylis-Hillman adduct. These observations might, therefore, suggest that aldehydes undergo preferentially the Baylis-Hillman reaction.
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0037029772
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It is worth mentioning here the work of Zaidlewich and co-workers, who reported an interesting enolization-aldolization of cyclohex-2-enone derivatives via dienolborinates. During their studies they also observed the formation of Baylis-Hillman adducts in minor amounts in the case of dienolborinates derived from hindered cyclo-hexenones (3,4,5-trisubstituted cyclohexenone derivatives) along with major aldol adducts; see: Zaidlewicz, M.; Sokol, W.; Wojtczak, A.; Neumann, P.; Nissinen, M. Tetrahedron Lett. 2002, 43, 3525.
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Zaidlewicz, M.1
Sokol, W.2
Wojtczak, A.3
Neumann, P.4
Nissinen, M.5
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12a,b (a) Shi, M.; Feng, Y.-S. J. Org. Chem. 2001, 66, 406. (b) Shi, M.; Jiang, J.-K.; Cui, S.-C. Tetrahedron 2001, 57, 7343. (c) Shi, M.; Jiang, J.-K.; Feng, Y.-S. Org. Lett. 2000, 2, 2397.
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12a,b (a) Shi, M.; Feng, Y.-S. J. Org. Chem. 2001, 66, 406. (b) Shi, M.; Jiang, J.-K.; Cui, S.-C. Tetrahedron 2001, 57, 7343. (c) Shi, M.; Jiang, J.-K.; Feng, Y.-S. Org. Lett. 2000, 2, 2397.
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12a,b (a) Shi, M.; Feng, Y.-S. J. Org. Chem. 2001, 66, 406. (b) Shi, M.; Jiang, J.-K.; Cui, S.-C. Tetrahedron 2001, 57, 7343. (c) Shi, M.; Jiang, J.-K.; Feng, Y.-S. Org. Lett. 2000, 2, 2397.
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