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Some extremely interesting papers have recently been published regarding the stereoselectivity in the homocoupling of benzaldehyde tricarbonylchromium complexes in THF, and its dependence on the presence of HMPA as cosolvent: [11a] N. Tanigu-chi, N. Kaneta, M. Uemura, J. Org. Chem. 1996, 61, 6088-6089.
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27
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85086352830
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note
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4], 1a,b was obtained in 15% yield and a 35/65 synlanti ratio.
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28
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85086352290
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note
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2 and HMPA, only unsaturated products were detected by NMR spectroscopy.
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29
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23544453995
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Precomplexation of the reducing species before formation of the ketyl radical was demonstrated for some low-valent titanium-promoted couplings: A. Fürstner, B. Bogdanovic, Angew. Chem. Int. Ed. Engl. 1996, 35, 3442-3469.
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Fürstner, A.1
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30
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0345005526
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note
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4 completely inhibited the reaction, in agreement with our results (ref.[5a]).
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31
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85086352909
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note
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2: we never observed diol formation, but only desulfurization products together with substitution reaction at the aromatic ring in some particular substrates.
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32
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85086353686
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note
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2OH singlet of the corresponding alcohol (the most common by-product of these reactions).
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33
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37049082801
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33847089013
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37
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0344574434
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note
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We have no evidences about the reaction mechanism operating in the different cases. Figure 1 shows a nucleophilic addition of the ketyl radical to a carbonyl, but direct coupling of two ketyls or nucleophilic addition of a C,O-dianion to the C = O cannot be ruled out. Complexation and/or chelation by the different metal species complicates the picture. For details on the different mechanisms proposed for the coupling reaction and a stereochemical discussion, see ref.[1][4]
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38
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2442536248
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1H NMR spectra of diols 8a-c with those reported in the literature was ambiguous; see: T. Hirao, M. Asahara, Y. Muguruma, A. Ogawa, J. Org. Chem. 1998, 63, 2812-2813.
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39
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0345436617
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note
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Interestingly enough, 8b arises from the coupling of two different enantiomers (S* + R*) of rac-2-phenylpropanal.
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40
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0003942864
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Wiley, New York
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0012004037
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