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(b) An essentially similar conclusion concerning the involvement of a homochiral dimer catalyst was subsequently reached in the analysis of autocatalytic reactions caried out at -25°C: I. Sato, D. Omiya, H. Igarashi, K. Kato, Y. Ogi, K. Tsukiyama and K. Soai, Tetrahedron: Asymmetry, 2003, 14, 975-979.
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0344839091
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note
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The detailed solution structure of the Zn alkoxide product will be discussed in ensuing publications. For the moment, a racemic sample gives two superposable 1-H NMR spectra corresponding on the one hand to R,S-alkoxide and on the other to R,R- or S,S-alkoxide, exchange being slow on the NMR timescale at ambient temperature. The two may be readily distinguished in the aromatic region around 8.6 ppm, with the racemate at lower field.
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31
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4243511953
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Blackmond has carried out an extensive study of the precipitation phenomenon under catalytic turnover conditions
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private communication
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Professor D. G. Blackmond has carried out an extensive study of the precipitation phenomenon under catalytic turnover conditions; private communication.
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Professor, D.G.1
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32
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0344839076
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note
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2O results reported in Fig. 3 are 37(R), 20(R) and 90(S) ee.
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34
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0012789728
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This derivation is normally attributed to W. H. Mills, Chem. Ind., 1932, 750, but has a longer history described in Mislow's review (ref. 16).
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Mills, W.H.1
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Clarendon Press (OUP), Oxford
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ff. For a recent formal derivation see: K. Iwamoto, Phys. Chem. Chem. Phys., 2002, 4, 3975-3979 and papers by the author cited therein.
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Iwamoto, K.1
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0345270418
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note
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This differs from the interpretation offered in our original paper (ref. 9), but caution is warranted by the fact that DFT calculations indicate that the macrocyclic dimer postulated there is not the lowest energy structure by a significant margin.
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38
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0344839050
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note
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Representing an ideal, since the real system will involve continual spontaneous reactions that will diminish in significance as the autocalytic process gradually becomes dominant. The idea that the statistical enantiomeric excess in a stochastic mechanism is dependent on the initial pool provided by the background reaction is implicit in the discussions in ref. 9b and ref. 11.
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