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Enantioselective cyclization using boron cocatalysis has been achieved, see ref 15.
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Matched implies that the catalyst reinforces the natural diastereoselectivity of the substrate, and mismatched implies that the catalyst contradicts the natural diastereoselectivity.
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1H NMR techniques. In particular, the presence of a strong NOE (generally between 5% and 10%) for cis 2,6- and 2,5-disubstituted compounds was observed between protons adjacent to the heteroatom. The corresponding absence of this NOE confirmed the trans stereochemical assignment of the opposite diastereomer. Furthermore, since the absolute stereochemistry of the starting substrate is known, the absolute configuration of the newly created allylic stereogenic center is also known.
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(b) Evans, D. A.; Carter, P. H.; Carreira, E. M.; Prunet, J. A.; Charette, A. B.; Lautens, M. J. Am. Chem. Soc. 1999, 121, 7540.
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Evans, D.A.1
Carter, P.H.2
Carreira, E.M.3
Prunet, J.A.4
Charette, A.B.5
Lautens, M.6
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100
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0034600771
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(c) Ohmori, K.; Ogawa, Y.; Obitsu, T.; Ishikawa, Y.; Nishiyama, S.; Yamamura, S. Angew. Chem., Int. Ed. 2000, 39, 2290.
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Ohmori, K.1
Ogawa, Y.2
Obitsu, T.3
Ishikawa, Y.4
Nishiyama, S.5
Yamamura, S.6
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101
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33646741013
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note
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Higher overall yields were obtained when the hydroboration was performed before carbonylation.
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102
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0035932595
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Other routes have accomplished syntheses of similar pieces with the exocyclic olefin stereochemistry installed in 14 steps: (a) Vakalopoulos, A.; Lampe, T. F. J.; Hoffmann, H. M. R. Org. Lett. 2001, 3, 929.
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Org. Lett.
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Vakalopoulos, A.1
Lampe, T.F.J.2
Hoffmann, H.M.R.3
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103
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0034720959
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In 18 steps: (b) Hale, K. J.; Hummersome, M. G.; Bhatia, G. S. Org. Lett. 2000, 2, 2189.
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(2000)
Org. Lett.
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Hale, K.J.1
Hummersome, M.G.2
Bhatia, G.S.3
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104
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37049087824
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In 8 steps: (c) Munt, S. P.; Thomas, E. J. J. Chem. Soc., Chem. Commun. 1989, 8, 480.
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(1989)
J. Chem. Soc., Chem. Commun.
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Munt, S.P.1
Thomas, E.J.2
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