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, pp. 4712-4718
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Loren, S.D.1
Campion, B.K.2
Heyn, R.H.3
Tilley, T.D.4
Bursten, B.E.5
Luth, K.W.6
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90
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21044459440
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(c) Ru-alcohol complex: See ref 27a
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(c) Ru-alcohol complex: See ref 27a.
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91
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2942544978
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and references therein
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W-alcohol and Mo-alcohol complexes: Bullock, R. M. Chem. Eur. J. 2004, 10, 2366-2374 and references therein.
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(2004)
Chem. Eur. J.
, vol.10
, pp. 2366-2374
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Bullock, R.M.1
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92
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21044456421
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note
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The mixture was analyzed by chiral GC.
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93
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21044459763
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note
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13C NMR spectra in Supporting Information.
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94
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21044446339
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note
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See Experimental Section for details.
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95
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21044437003
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note
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The possible pathways for alkoxide exchange include: (i) ring slippage, (ii) alkoxide loss, (iii) CO loss, (iv) alkoxide attack at CO followed by alkoxide loss.
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96
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21044443698
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note
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As shown in Figure 3, the racemization of (S)-9 catalyzed by complexes 3a-c can be performed by the use of only 0.5 mol % of catalyst with short reaction times. In sharp contrast, the racemization of (S)-9 catalyzed by 1 mol % of ruthenium hydride 8 (in the presence of 1 mol % acetophenone) required very long reaction times (1.5 days). Only when 5 mol % of ruthenium hydride 8 was used (in the presence of 5 mol % of acetophenone) could shorter reaction times be realized but still with an induction period of 2.5 h (Figure 5).
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97
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0012477017
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2H reacts very slowly with benzaldehyde: Casey, C. P.; Vos, T. E.; Singer, S. W.; Guzei, I. A. Organometallics 2002, 21, 5038-5046.
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(2002)
Organometallics
, vol.21
, pp. 5038-5046
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Casey, C.P.1
Vos, T.E.2
Singer, S.W.3
Guzei, I.A.4
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98
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0000782830
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(a) Guari, Y.; Sabo-Etienne, S.; Chaudret, B. J. Am. Chem. Soc. 1998, 120, 4228-4229.
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(1998)
J. Am. Chem. Soc.
, vol.120
, pp. 4228-4229
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Guari, Y.1
Sabo-Etienne, S.2
Chaudret, B.3
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100
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21044433534
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note
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Other conceivable mechanisms are hydride migration to the cyclopentadienyl ring and hydride migration to CO to give a formyl intermediate. We are currently investigating the mechanism of this remarkable C-H bond cleavage in our laboratories.
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101
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21044453255
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note
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If the ketone from β-elimination were only π-bonded no racemization could take place, since the hydride would readd to the same enantioface from which it was eliminated.
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102
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21044442469
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note
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An interesting question is why the ring slippage readily occurs for the alkoxide in β-elimination and not for the hydride in its reaction with a ketone. This is probably due to that the ketone is not nucleophilic enough to induce a ring slip. In the alkoxide the C-H can interact with ruthenium and induce a push of electrons to favor the ring slip.
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