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19
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85029982642
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note
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2) did not promote reaction at all; with 2.0 equiv. reaction was observed, but without significant stereoselectivity. It seems likely that the first equivalent of Lewis acid is irreversibly sequestered by formation of a 5-ring chelate between the benzyl and methyl ethers in this case, thus preventing the desired chelation between the aldehyde oxygen and the methyl ether moieties. Use of the TBS silyl ether precludes the undesired sense of complexation.
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20
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0001370202
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b) Keck, G. E.; Andrus, M. B.; Castellino, S. J. Am. Chem. Soc. 1989, 111, 8136.
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0004042577
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Schinzer, D., Ed.; NATO ASI Series; Kluwer Academic Publishers: Dordrecht, The Netherlands; Chapter 5
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d) Keck, G. E.; Castellino, S.; Andrus, M. B. Selectivities in Lewis Acid Promoted Reactions; Schinzer, D., Ed.; NATO ASI Series; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1989; Chapter 5.
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Selectivities in Lewis Acid Promoted Reactions
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Keck, G.E.1
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Andrus, M.B.3
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23
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85029985529
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note
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3 substituent is due to allylic strain.
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25
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0006934277
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c) Keck, G. E.; Castellino, S.; Wiley, M. R. J. Org. Chem. 1986, 51, 5478.
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26
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0001218374
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For descriptions of "chelation" vs "non-chelation" controlled reactions and 1,3 asymmetric induction, see: a) Reetz, M. T.; Harms, K.; Reif, W. Tetrahedron Lett. 1988, 29, 5881.
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c) Reetz, M. T.; Kesseler, K.; Jung, A. Tetrahedron 1984, 40, 4327.
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0001293261
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For a closely related example, see: Nicolaou, K. C.; Claremon, D. A.; Barnette, W. E. J. Am. Chem. Soc. 1980, 102, 6611.
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Nicolaou, K.C.1
Claremon, D.A.2
Barnette, W.E.3
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Keck, G.E.1
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Weglarz, M.A.3
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34
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85029991031
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note
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13C NMR; 160.9, 159.1, 140.5, 138.7, 137.2, 137.0, 135.9, 131.1, 129.3, 124.2, 120.2, 114.4, 113.7, 96.8, 88.7, 79.5, 76.5, 70.7, 56.3, 55.6, 55.3, 53.4, 41.1, 37.5, 32.3, 14.8, 14.4, 13.9, 12.1, 10.0.
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