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For known, difficult-to-obtain silanes with silicon-centered chirality, see: a) D. N. Roark, L. H. Sommer, J. Am. Chem. Soc. 1974, 95, 969-971;
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0011390346
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Besides the methods discussed herein, an access based on a reductive enzymatic kinetic resolution of acyl silanes is available: a) R. Tacke, S. Brakmann, F. Wuttke, J. Fooladi, C. Syldatk, D. Schomburg, J. Organomet. Chem. 1991, 403, 29-41;
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0011481427
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To the best of our knowledge, a single kinetic resolution process of racemic silyl ethers based on the reductive cleavage of the silicon-oxygen bond by chiral hydride reagents has been reported so far. However, enantiomeric excesses were determined from the optical rotatory power, which emerges as being sensitive towards impurities of the chiral ligand. In our hands, application of this method to a derivative of rac-5 provided only marginal optical enrichment (< 1% ee): a) A. Holt, A. W. P. Jarvis, G. J. Jarvis, Tetrahedron Lett. 1968, 4087-4088;
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37
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33746701748
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note
-
A catalytic asymmetric access as depicted in Scheme 2 was not considered since the synthesis of the requisite precursor, 1,2,3,4-tetrahydro-1- silanaphthalene, has not been accomplished yet.
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38
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0347881377
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Early reports of related cyclizations: a) H. Gilman, O. L. Marrs, J. Org. Chem. 1964, 29, 3175-3179;
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2742593739
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0000831235
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Acceleration by copper(I) cyanide for otherwise sluggish Grignard reactions has been reported: P. J. Lennon, D. P. Mack, Q. E. Thompson, Organometallics 1989, 8, 1121-1222.
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Lennon, P.J.1
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42
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33746710741
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Diploma Thesis, Albert-Ludwigs-Universität, Freiburg
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U. K. Schmid, Diploma Thesis, Albert-Ludwigs-Universität, Freiburg, 2003.
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a) M. Ishizaki, K. Fujita, M. Shimamoto, O. Hoshino, Tetrahedron: Asymmetry 1994, 5, 411-424;
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45
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76349119731
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2BCl provided only poor yields and 94% ee: C. Bolm, M. Ewald, M. Felder, G. Schlinghoff, Chem. Ber. 1992, 125, 1169-1190.
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0033552259
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In analogy to a previously reported procedure: D. H. Appella, Y. Moritani, R. Shintani, E. M. Ferreira, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 9473-9474.
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0000816349
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[29b] has been previously used: a) C. Lorenz, U. Schubert, Chem. Ber. 1995, 128, 1267-1269;
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48
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0001324442
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b) D. M. Bestrensky, D. E. Huseland, C. McGettigan, J. M. Stryker, Tetrahedron Lett. 1988, 29, 3749-3752.
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49
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33746702990
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note
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[27]
-
-
-
-
50
-
-
33746718474
-
-
note
-
[7] is reproduced incorrectly.
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-
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