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For earlier reports on Lewis or Bronsted acid-catalyzed crotylboration, see: a
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Following the Cahn - Ingold - Prelog priority rules, the parent Z- and E-crotylboronates become E- and Z-, respectively (E-1 and E-5, and Z-1 and Z-5), when substituted with a COOMe group. Cahn, R. S.; Ingold, C.; Prelog, V. Angen: Chem., Int. Ed. Engl. 1966, 5, 385.
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25
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33947468884
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It should be remembered that the parent Z- and E-crotylboronates give cis-and trans-d-methyl homoallyl alcohols, respectively, via a six-membered Zimmerman-Traxler transition state. Zimmerman, H. E, Traxler, M. D. J. Am. Chem. Soc. 1957, 79, 1920
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(b) It should be remembered that the parent Z- and E-crotylboronates give cis-and trans-d-methyl homoallyl alcohols, respectively, via a six-membered Zimmerman-Traxler transition state. Zimmerman, H. E.; Traxler, M. D. J. Am. Chem. Soc. 1957, 79, 1920
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3-catalyzed reaction provided a cis/trans lactone ratio of 99:1.
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3-catalyzed reaction provided a cis/trans lactone ratio of 99:1.
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Reagents such as E- and Z-5 have been termed "higher crotylboranes", see: Brown, H. C.: Narla, G. Tetrahedron Lett. 1997, 38, 219.
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34
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18044396543
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For the Lewis acid-catalyzed conversion of β- to δ-substituted homoallylic alcohols, see: a
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For the Lewis acid-catalyzed conversion of β- to δ-substituted homoallylic alcohols, see: (a) Nokami, J.; Yoshizane, K.; Matsuura, H.; Sumida, S. J. Am. Chem. Soc. 1998, 120, 6609.
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41
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34250656764
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Addition of a different aldehyde (2d) to the intermediate syn-8, obtained from the allylboration of 2a with E-1 under refluxing conditions, provided a mixture of lactones cu-4a and E-3d.
-
Addition of a different aldehyde (2d) to the intermediate syn-8, obtained from the allylboration of 2a with E-1 under refluxing conditions, provided a mixture of lactones cu-4a and E-3d.
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42
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34250618098
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11B NMR spectroscopy (δ 22 ppm, see the experimental details in the Supporting Information),
-
11B NMR spectroscopy (δ 22 ppm, see the experimental details in the Supporting Information),
-
-
-
-
43
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34250657825
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The PMR spectra of the progress of the reaction for the formation of the rearranged product E-3a is also provided in the Supporting Information.
-
(b) The PMR spectra of the progress of the reaction for the formation of the rearranged product E-3a is also provided in the Supporting Information.
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