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For recent examples of this type of external heavy-atom effect, see: Z. S. Romanova, K. Deshayes, P. Piotrowiak, J. Am. Chem. Soc. 2001, 123, 2444-2445; M. A. Anderson, Y. Xu, B. Grissom, J. Am. Chem. Soc. 2001, 123, 6720-6721.
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(2001)
J. Am. Chem. Soc.
, vol.123
, pp. 2444-2445
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Romanova, Z.S.1
Deshayes, K.2
Piotrowiak, P.3
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68
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0034809352
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For recent examples of this type of external heavy-atom effect, see: Z. S. Romanova, K. Deshayes, P. Piotrowiak, J. Am. Chem. Soc. 2001, 123, 2444-2445; M. A. Anderson, Y. Xu, B. Grissom, J. Am. Chem. Soc. 2001, 123, 6720-6721.
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(2001)
J. Am. Chem. Soc.
, vol.123
, pp. 6720-6721
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Anderson, M.A.1
Xu, Y.2
Grissom, B.3
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69
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0033623690
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For a leading reference, see: M. Newcomb, Acc. Chem. Res. 2000, 33, 449-455.
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(2000)
Acc. Chem. Res.
, vol.33
, pp. 449-455
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Newcomb, M.1
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70
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2142733708
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note
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[41]
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71
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2142680669
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unpublished results
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For example, we previously found that α-methylstyrene gave poor epoxide yields and low ee with complex 14: C. Bousquet, D. G. Gilheany, unpublished results.
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Bousquet, C.1
Gilheany, D.G.2
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72
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2142789334
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note
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[5a]
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73
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33845279269
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Although 15 was unknown, the analogous tetraphenyl-substituted alkene has previously been used in the investigation of epoxidation by Cytochrome P-450 models: A. J. Castellino, T. C. Bruice, J. Am. Chem. Soc. 1988, 110, 7512-7519; M.-H. Le Tadic-Biadatti, M. Newcomb, J. Chem. Soc. Perkin Trans. 2 1996, 1467-1473.
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(1988)
J. Am. Chem. Soc.
, vol.110
, pp. 7512-7519
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Castellino, A.J.1
Bruice, T.C.2
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74
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0000557555
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Although 15 was unknown, the analogous tetraphenyl-substituted alkene has previously been used in the investigation of epoxidation by Cytochrome P-450 models: A. J. Castellino, T. C. Bruice, J. Am. Chem. Soc. 1988, 110, 7512-7519; M.-H. Le Tadic-Biadatti, M. Newcomb, J. Chem. Soc. Perkin Trans. 2 1996, 1467-1473.
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(1996)
J. Chem. Soc. Perkin Trans. 2.
, pp. 1467-1473
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Le Tadic-Biadatti, M.-H.1
Newcomb, M.2
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75
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2142849976
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note
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A complication with alkene 15 is the presence of four chiral centers. The two E isomers were distinguishable from the two Z isomers by NMR spectroscopy, and all four were distinguishable by GC. Due to a lack of a large-scale method of separation, 15 was used as the 1:1 mixture of E and Z isomers obtained from the Wittig reaction used for its synthesis.
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77
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note
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1H NMR spectroscopy of the crude reaction mixtures showed that the E alkene reacted somewhat faster, since when the E alkene had been consumed, 11% of the Z isomer remained.
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78
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2142839787
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note
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1H NMR spectrum of the crude product the only new signals identifiable were in the methylene (broad multiplet: δ = 1.6) and aldehyde (singlet: δ = 10.0) regions.
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