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A preliminary survey of ketone enolates did not yield satisfactory results; for example, 2-(trimethylsilyloxy)propene underwent addition to isoquinoline in the presence of TrocCl and 1 to yield the corresponding dihydroisoquinoline in 14% ee (unoptimized).
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58
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27444447317
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note
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A list of solvents and other catalysts tested may be found in the Supporting Information.
-
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59
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0004150157
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University of Göttingen, Germany
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2 (SHELXL-97); all non-hydrogen atoms were refined anisotropically; the positions of hydrogen atoms were found by difference Fourier methods and refined isotropically. CCD-275454 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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A neutral chloroamide structure, rather than an ion pair, may represent a more accurate depiction of the bonding interactions in N-acyliminium chlorides in nonpolar organic solvents (for an NMR spectroscopic study that supports this assertion, see: A. K. Bose, G. Spiegelman, M. S. Manhas, Tetrahedron Lett. 1971, 3167-3170). Calculations that use the density-functional theory (Chemical Equation Presented) (B3LYP/6-31G + + (d,p)) predict substantial chloroamide character for N-acylisoquinolinium chloride
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65
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27444447223
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note
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Transesterification of the resulting product permitted the absolute configuration to be assigned (see the Supporting Information for details).
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