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For recent C-C couplings using Fe(0) complexes, see: (a) Terent'ev, A. B.; Vasil'eva, T. T.; Kuz'mina, N. A.; Mysova, N. E.; Chakhovskaya, O. V. Russ. J. Org. Chem. 2001, 37, 1273.
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Rieke, R.D.1
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34
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33749994643
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note
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Fe(0) powder (< 10 μm, 99.9%) was purchased from Aldrich and Alfa Aeser and stored/handled under an inert atmosphere to minimize formation of an oxide coating.
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35
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0141506890
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Wang, L.; Li, P. H.; Wu, Z. T.; Yan, J. C.; Wang, M.; Ding, Y. B. Synthesis 2003, 2001.
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Wang, L.1
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Ding, Y.B.6
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37
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0035913734
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Control experiments indicate that 23 and 25 are stable under the reaction conditions. We speculate the minor amounts of debrominated byproducts arise via double metalation of the initial Reformatsky-type adduct i to give ii. We and others have previously invoked the generation of gemdichromium intermediates: Baati, R.; Barma, D. K.; Falck, J. R.; Mioskowski, C. J. Am. Chem. Soc. 2001, 123, 9196. The greater reactivity of bromides makes this process partially competitive with the pathway in Figure 1 (Diagram presented)
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Baati, R.1
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38
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22244478590
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2, see: Concellon, J. M.; Concellon, C.; Mejica, C. J. Org. Chem. 2005, 70, 6111.
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39
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33750002189
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note
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In sharp contrast, reactions of methyl tribromoacetate with ketones afforded complex product mixtures. This may reflect its greater steric profile and/or the proclivity of the more reactive bromides toward undesired side reactions.
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40
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0030605827
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(a) Rodebaugh, R.; Debenham, J. S.; Fraser-Reid, B. Tetrahedron Lett. 1996, 37, 5477.
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42
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33749992024
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note
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Considering standard reduction potentials of Fe(II)/Fe (-0.45 V), Fe(III)/Fe (-0.04 V), and Fe(III)/Fe(II) (+0.77 V) compared to Cr(III)/Cr(II) (-0.41 V), we postulate the formation of Fe(II) salts in the tandem Reformatsky elimination reaction.
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43
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33750031932
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note
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2O, 0 °C, 20 min) of the ester and 2D nOe analysis of the resultant primary alcohols; comparable treatment of 42 gave an unstable product, so its stereochemistry could not be established.
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44
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0001649364
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1d in accordance with literature data (Takai, K.; Hotta, Y.; Oshima, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1980, 53, 1698) but now must be revised as (E)-34 based upon the above nOe experiments.
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Takai, K.1
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46
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0000144592
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Heathcock, C. H., Ed.; Elsevier: Amsterdam
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(a) Rathke, M. W.; Weipert, P. In Comprehensive Organic Synthesis; Heathcock, C. H., Ed.; Elsevier: Amsterdam, 1991; Vol. 2, p 277.
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Rathke, M.W.1
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