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The reversible photomodulation of catalytic activity has thus far been poorly explored. Most reported examples suffer from a lack of generality and lowon/off ratios: a) A. Ueno, K. Takahashi, T. Osa, J. Chem. Soc. Chem. Commun. 1980, 837-838;
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Chemical amplification by photochemically generated acids, which catalyze chemical transformations that alter the solubility of polymeric materials, constitutes the basis of modern resist technology in the semiconductor industry: a J. M. J. Fréchet, C. G. Willson, H. Ito, US Patent 4,491,628, 1985;
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Chemical amplification by photochemically generated acids, which catalyze chemical transformations that alter the solubility of polymeric materials, constitutes the basis of modern resist technology in the semiconductor industry: a) J. M. J. Fréchet, C. G. Willson, H. Ito, US Patent 4,491,628, 1985;
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53549118738
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For an example of a Ru-based catalyst for photoinduced ringopening-metathesis polymerization (ROMP) see: D. Wang, K. Wurst, W. Knolle, U. Decker, L. Prager, S. Naumov, M. R. Buchmeiser, Angew. Chem. 2008, 120, 3311-3314;
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For an example of a Ru-based catalyst for photoinduced ringopening-metathesis polymerization (ROMP) see: D. Wang, K. Wurst, W. Knolle, U. Decker, L. Prager, S. Naumov, M. R. Buchmeiser, Angew. Chem. 2008, 120, 3311-3314;
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Irreversibly photogenerated bases were first described by Cameron and Fréchet: a) J. F. Cameron, J. M. J. Fréchet, J. Org. Chem. 1990, 55, 5919-5922;
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Further studies were carried out at Ciba Specialty Chemicals; see, for example: d J.-L. Birbaum, M. Kunz, A. Kimura, H. Kura, H. Oka, H. Nakashima, Eur. Pat. Appl. 898202, 1999;
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Further studies were carried out at Ciba Specialty Chemicals; see, for example: d) J.-L. Birbaum, M. Kunz, A. Kimura, H. Kura, H. Oka, H. Nakashima, Eur. Pat. Appl. 898202, 1999;
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53549118443
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See the Supporting Information for details
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See the Supporting Information for details.
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38
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0003942864
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For a discussion of the conformational behavior of piperidines, see:, Wiley, New York, and references therein
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For a discussion of the conformational behavior of piperidines, see: E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds, Wiley, New York, 1994, pp. 740, and references therein.
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Eliel, E.L.1
Wilen, S.H.2
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39
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53549100054
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CCDC 686676 ((E)-4b), and 686677 ((Z)-4b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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CCDC 686676 ((E)-4b), and 686677 ((Z)-4b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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40
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53549087384
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Detailed experimental and theoretical investigations concerning the conformational behavior in solution will be described elsewhere
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Detailed experimental and theoretical investigations concerning the conformational behavior in solution will be described elsewhere.
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42
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0035804426
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and references therein. for a review, see: b
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for a review, see: b) F. A. Luzzio, Tetrahedron 2001, 57, 915-945, and references therein.
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Luzzio, F.A.1
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43
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53549086549
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To obtain accurate kinetic data, we used catalysts 4a-c in their isolated form, that is, either as the pure E isomer or as a mixture of Z and E isomers in the photostationary state.
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To obtain accurate kinetic data, we used catalysts 4a-c in their isolated form, that is, either as the pure E isomer or as a mixture of Z and E isomers in the photostationary state.
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44
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53549120060
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Note added in proof: After submission of this manuscript photomodulation of the Lewis acidity of dithienylethene-based boronates has been reported in: V. Lemieux, M. D. Spantulescu, K. M. Baldrigde, N. R. Branda, Angew. Chem. 2008, 120, 5112-5115;
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Note added in proof: After submission of this manuscript photomodulation of the Lewis acidity of dithienylethene-based boronates has been reported in: V. Lemieux, M. D. Spantulescu, K. M. Baldrigde, N. R. Branda, Angew. Chem. 2008, 120, 5112-5115;
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45
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Angew. Chem. Int. Ed. 2008, 47, 5034-5047.
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