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A recent article demonstrated increased reactivity in direct aldol reactions catalyzed by proline modified by replacing the carboxylic acid function with a tetrazolic acid: Hartikka, A.; Arvidsson, P. I. Tetrahedron: Asymmetry 2004, 15, 1831.
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0037184431
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For a description of the use of reaction calorimetry in kinetic analysis, see: Singh, U.K.; Stricter, E. R.; Blackmond, D. G.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 14104.
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17
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4644330928
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note
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Product ee = 93% was maintained 3 h after completion of reactions as in Figure 1a at 278 K; after 12 h at 278 K, ee = 89%.
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18
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33845551868
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(a) Seebach, D.; Boes, M.; Naef, R.; Schweizer, W. B. J. Am. Chem. Soc. 1983, 105, 5390.
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84986516466
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(b) Orsini, F.; Pelizzoni, F.; Forte, M.; Jisti, M.; Bombieri, G.; Benetollo, D. J. Heterocycl. Chem. 1989, 26, 837.
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(c) List, B.; Hoang, L.; Martin, H. J. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5839.
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List, B.1
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21
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4644315223
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note
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Under typical low-temperature reaction conditions, decomposition of 5 back to proline and product 3 must be slow, since racemization of 3 is not observed at 278 K on the time scale of the reaction.
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22
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4644366076
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note
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3CN results in rapid precipitation of proline.
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