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The rigid 9-BBN moiety had proven to be less sensitive to steric factors than of dialkylboryl in hydroboration reactions, see: Smith, K.; Pelter, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; 8, Chapter 3, p 703.
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The rigid 9-BBN moiety had proven to be less sensitive to steric factors than of dialkylboryl in hydroboration reactions, see: Smith, K.; Pelter, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 8, Chapter 3, p 703.
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46
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For examples of the reaction stereoselectivity switch by boryl geometry (n-Bu2B-OTf vs 9-BBN-OTf, see: (a) Inoue, T, Uchimaru, T, Mukaiyama, T. Chem. Lett. 1977, 153
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2B-OTf vs 9-BBN-OTf), see: (a) Inoue, T.; Uchimaru, T.; Mukaiyama, T. Chem. Lett. 1977, 153.
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The stereochemical outcome of metal-mediated aldol and related reactions has previously been interpreted employing the open transition state, see: (a) Oare, D, Heathcock, C. H. Topics in Stereochemistry; Eliel, E. L, Wilen, S. H, Eds, John Wiley and Sons: New York, 1991; 20, pp 161-165
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The stereochemical outcome of metal-mediated aldol and related reactions has previously been interpreted employing the open transition state, see: (a) Oare, D.; Heathcock, C. H. Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; John Wiley and Sons: New York, 1991; Vol. 20, pp 161-165.
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76049092108
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While complete conversion to aldol adducts 7 occurred within 20 min at -90 to -70°C, the corresponding aldol addition of valine-based enolate 2 with Lewis acid-precomplexed aldehyde required 4 h at -78°C. This differential reactivity is important to the high-yield anti-stereoselective aldolization of boryl enolate 6
-
While complete conversion to aldol adducts 7 occurred within 20 min at -90 to -70°C, the corresponding aldol addition of valine-based enolate 2 with Lewis acid-precomplexed aldehyde required 4 h at -78°C. This differential reactivity is important to the high-yield anti-stereoselective aldolization of boryl enolate 6.
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