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30744446920
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note
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4 + H, 282.1705, found 282.1707).
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20
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0001553952
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21
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30744445660
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note
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Calculations were performed using a Cache Worksystem Pro Version 6.1.12.33 software from Fujitsu Limited.
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23
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25
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30744435563
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note
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MAD: methyl(bis(2,6-di-tert-butyl-4-methylphenoxy))aluminum; MAPh: methyl(bis(2,6-diphenylphenoxy))aluminum.
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27
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30744449932
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Hurd, A.R.1
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28
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30744469823
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note
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The relative configurations of 30a und 30b were not determined because this route was abandoned.
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30
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33751391619
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(b) Danheiser, R. L.; Dixon, B. R.; Gleasont, R. W. J. Org. Chem. 1992, 57, 6094-6097.
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39
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30744470083
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note
-
Nitroblefin 26 was formed as a mixture of isomers at the unsaturated ester double bond (E/Z ∼ 20/1). It is possible that the cycloaddition of 26 was completely stereoselective and the 20/1 ratio of the diastereometric nitroso acetals reflects the presence of the two isomers in the starting material. In this case, the minor cycloadduct may be the epimer of 38a at the ester-group-bearing stereocenter.
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-
40
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30744446183
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note
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The crystallographic coordinates of 38a have been deposited with the Cambridge Crystallographic Data Centre: deposition no. CCDC 275186. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Rond, Cambridge CB2 IEZ, UK.; fax: (4-44) 1223-336-033; or deposit@ccdc.cam.ac.uk). For the Chem3D image, see the Supporting Information.
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30744432324
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note
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For a summary of recent strained and troublesome lactamizations, see ref 4.
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-
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59
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30744465792
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note
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In each case, to locate the saddle point, an energy surface map was calculated in the gas phase starting with the corresponding nitronate (bound to a molecule of trimethylaluminum) and systematically varying the C-C and N-O bond length. Frequency calculations were used to confirm the nature of the saddle points. All transition structures had only one imaginary frequency corresponding to the formation of the expected bonds. Reaction coordinate calculations were performed to determine the connections of the cycloaddition transition structures with the reactants and the products.
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