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3
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29844458256
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note
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Stereogenicity is defined as the property of a given structural unit to generate stereoisomers upon exchange of ligands at that unit (see ref. 1).
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4
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29844435608
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Chirality is the property of any object that is not superposable on its mirror image:K. Mislow, Top. Stereochem., 1998, 22, 1-82.
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Mislow, K.1
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5
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84981828672
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(a) A clear demonstration of how deeply this confusion has affected stereochemistry is found in the title that Cahn, Ingold, and Prelog selected for their 1966 paper on stereochemical descriptors ("Specification of Molecular Chirality"). The R/S and related symbols clearly describe the spatial disposition of ligands around stereogenic units rather than chirality, see: R. S. Cahn, C. K. Ingold and V. Prelog, Angew. Chem., Int. Ed. Engl., 1966, 5, 385-415;
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Cahn, R.S.1
Ingold, C.K.2
Prelog, V.3
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6
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37049160530
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(b) Perplexingly, the previous papers correctly referred to the specification of configuration, a stereogenic property; see: R. S. Cahn and C. K. Ingold, J. Chem. Soc., 1951, 612-622, and;
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Cahn, R.S.1
Ingold, C.K.2
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34250557159
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R. S. Cahn, C. K. Ingold and V. Prelog, Experientia, 1956, 12, 81-94.
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84991478978
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One might think that this is a purist's stance in an attempt to rid chemical language of metaphor. Au contraire, metaphor should be welcomed into our world and used to enrich our ability to communicate. For a recent discussion of the use of metaphor in chemical communication, see:H. L. Kretzenbacher, HYLE-Int. J. Philos. Chem., 2003, 9, 191-218.
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Racemization does not necessarily imply formation of an achiral species: (a) K. Mislow, Science, 1954, 120, 232-233;
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J.-C. Chambron, J.-P. Sauvage and K. Mislow, J. Am. Chem. Soc., 1997, 119, 9558-9559. Obviously, a molecule in a racemate is as chiral as its counterpart in the enantiopure form.
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Chambron, J.-C.1
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29844442840
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note
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This disregards the remote possibility of spontaneous resolution of the product.
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34
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0019277205
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Notably, this kind of result has been observed previously and fully rationalized without referring to "MoC": (a) M. F. Brafia, M. Garrido, M. L. Lopez and A. M. Sanz, J. Heterocycl. Chem., 1980, 17, 829-830;
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Brafia, M.F.1
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37049069871
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85163172201
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This effect has been known for a long time as the "Pfeiffer effect": P. Pfeiffer and K. Quehl, Ber. Dtsch. Chem. Ges., 1931, 64, 2667-2671.
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0036470549
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