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77956467039
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The methoxy groups at C-2′ and C-3 were easily distinguished by 2D HSQC and HMBC correlations
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The methoxy groups at C-2′ and C-3 were easily distinguished by 2D HSQC and HMBC correlations.
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56
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0003536850
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77956489778
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Using a modified Karplus-type calculation as implemented in Maestro, version 9.0, Schrödinger, LLC, New York, NY
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Using a modified Karplus-type calculation as implemented in Maestro, version 9.0, Schrödinger, LLC, New York, NY, 2009.
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(2009)
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60
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77956495142
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Details on the preparation of these models are provided in the Supporting Information section
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Details on the preparation of these models are provided in the Supporting Information section.
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61
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A part of the present work has been published as a preliminary communication
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77956489344
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For convenience, the atom-numbering system used throughout this section and in the NMR assignments is the one depicted in the corresponding Scheme although a IUPAC systematic nomenclature has been used in the Experimental and Supporting Information sections
-
For convenience, the atom-numbering system used throughout this section and in the NMR assignments is the one depicted in the corresponding Scheme although a IUPAC systematic nomenclature has been used in the Experimental and Supporting Information sections.
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The high propensity of mannopyranosyl radicals for quenching by stannanes along the axial direction and formation of equatorial glycosides is well established. See, for example:, and references cited therein
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The high propensity of mannopyranosyl radicals for quenching by stannanes along the axial direction and formation of equatorial glycosides is well established. See, for example: D. Crich, S. Sun, J. Brunckova, J. Org. Chem. 1996, 61, 605-615 and references cited therein.
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77956478597
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Radical-mediated intermolecular brominations can discriminate between H-5′ and H-1′, but the regioselectivity of the reaction is largely dependent on the anomeric substituent and configuration, as well as the halogenating agent used. In consequence, the regioselectivity results observed in these intermolecular reactions are not easily extrapolated to our models. In fact, a closely related compound, methyl 2, 3, 4, 6-tetra-O-acetyl-α-D- mannopyranoside, does not give any bromination and most of it was recovered unchanged after prolonged reaction times a
-
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