Intramolecular trapping of an intermediate in the reduction of imines by a hydroxycyclopentadienyl ruthenium hydride: Support for a concerted outer sphere mechanism

Journal of the American Chemical Society

Volumn 129, Issue 38, 2007, Pages 11821-11827

  Casey, Charles P ^a   Clark, Timothy B ^a   Guzei, Ilia A ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; MOLECULAR INTERACTIONS; REDUCTION; RUTHENIUM;

INTRAMOLECULAR AMINE; INTRAMOLECULAR TRAPPING AMINE; RUTHENIUM AMINE COMPLEXES;

AMINES;

AMINE; CYCLOPENTADIENE DERIVATIVE; HYDROGEN; IMINE; NITROGEN; RUTHENIUM DERIVATIVE; TOLUENE;

ARTICLE; CHEMICAL STRUCTURE; COMPLEX FORMATION; DENSITY FUNCTIONAL THEORY; KINETICS; REDUCTION;

AMINES; HYDROGEN; IMINES; KINETICS; MOLECULAR CONFORMATION; ORGANOMETALLIC COMPOUNDS; OXIDATION-REDUCTION; RUTHENIUM; STEREOISOMERISM; TOLUENE;

EID: 34748911400     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja073370x     Document Type: Article

References (42)

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28. 12
29. 2 to ruthenium. This suggests that ruthenium migration via the aromatic system might be possible.
30. 10 of an intermolecular trapping of an intermediate in the reduction of an imine by 1′ in the presence of an amine.
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33. a = 5.29, N = 16.53 in water), but is 3.54 N units less nucleophilic. Brotzel, F.; Chu, Y. C.; Mayr, H. J. Org. Chem. 2007, 72, 3679-3688.
34. 10
35. 15N NMR integrals.
36. 10
37. 15N NMR chemical shifts are reported on the δ scale with respect to nitrobenzene as the standard.
38. See the Supporting Information.
39. 15N.
40. 15N-23). See the Supporting Information.
41. For a more detailed discussion of benzylamine as an intermolecular trap in the reduction of imine 12 by 1, see the Supporting Information.
42. 15N,N from intermediate E″ could also proceed directly from E″ to the respective amine complex without a hydrogen-bonded intermediate [D″ or F″ (analogous to F′ in Scheme 6)]. This variation in the mechanism does not change the conclusions described in the text.