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For trans-1,2-diaminocyclitols from N-tosyl or N-acyl aziridines see: (a) Reference 7.
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For the sake of simplicity, the synthetic methodology described in this work has been carried out from the easily available racemic tetra-O- benzylconduritol B epoxide 9, obtained from (±)-conduritol B by epoxidation (MCPBA, MeOH) followed by benzylation (BnBr, NaH, DMF). For the synthesis of enantiopure 9, see ref 22. For general syntheses of enantiopure conduritol B epoxide derivatives from the chiral pool, see: (a) Falshaw, A.; Hart, J. B.; Tyler, P. C. Carbohydr. Res. 2000, 329, 301-308.
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25444504726
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note
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In all cases, the major conformation is assumed to be that imposed by the "all-equatorial" disposition of the OBn groups.
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52
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For epoxide opening under nonchelating conditions, see, inter alia: (a) Uzan, R.; Letellier, P.; Ralainairina, R.; Beaupère, D. Synthesis 1994, 925-930.
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25444485358
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note
-
Formation of minor amounts of azido alcohol 16 had already been observed in reaction of mesylate 14 with other nucleophiles in DMF (unpublished results from our group).
-
-
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57
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84989453187
-
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Imidate esters salts have been proposed as reaction intermediates for the conversion of alcohols into formate esters. See, for example: (a) Barluenga, J.; Campos, P. J.; González-Núñez, E.; Asensio, G. Synthesis 1985, 426-428.
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25444458763
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note
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Mesylate 15 also failed to react with other nucleophiles, such as sodium azide, potassium phthalimide (see text), or benzoic acid/CsF, whereas the corresponding triflate A gave the anti elimination adduct B. Diagram presented
-
-
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62
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0027370483
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For related examples of the effect of stereoelectronic effects on the reactivity of inositol derivatives, see: (a) Guidot, J. P.; Legall, T. J. Org. Chem. 1993, 58, 5271-5273.
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For a similar process, see: Rohloff, J. C.; Kent, K. M.; Postich, M. J.; Becker, M. W.; Chapman, H. H.; Kelly, D. E.; Lew, W.; Louie, M. S.; McGee, L. R.; Prisbe, E. J.; Schultze, L. M.; Yu, R. H.; Zhang, L. J. J. Org. Chem. 1998, 63, 4545-4550.
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66
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25444486314
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note
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The reactivity of mesylate 14 with nonanionic nitrogen nucleophiles was somewhat sluggish. Thus, no reaction was observed with butylamine or diethylamine under forcing conditions (10 equiv, DMF, 90 °C, 48 h, sealed tube). On the contrary, reaction of 14 with sodium azide (DMF, 100 °C) afforded the expected cis-diazide, whose spectroscopic data matched those described in the literature (ref 18).
-
-
-
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67
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25444474641
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note
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The relative configuration present in mesylates 14 and 26, in which the mesyloxy group shows a trans relationship with respect to both of the substituents on the adjacent carbon atoms, seems to be the only one operative for intermolecular substitution with anionic nitrogen nucleophiles. Compare, for example, the reactivity of the above mesylates with that of diastereomeric mesylate 15 (see text) or triflate A, as indicated in ref 30.
-
-
-
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68
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0141632606
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For a similar sequence leading to differently functionalized N,N′-cis-1,2-diaminocyclohexane derivatives, see: Govindaraju, T.; Gonnade, R. G.; Bhadbhade, M. M.; Kumar, V. A.; Ganesh, K. N. Org. Lett. 2003, 5, 3013-3016.
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25444522547
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Bidimensional nOe experiments from azido N-octanoyl derivative 35 were also in agreement with the stereochemical assignment for precursor azido amine 23 (see Supporting Information).
-
-
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71
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0742269730
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Polybenzylated aminocyclitols have been reported to be poisonous for the Pd/C catalysed hydrogenolysis of benzyl ethers (Surfraz, M. B. U.; Akhtar, M.; Allemann, R. K. Tetrahedron Lett. 2004, 45, 1223-1226).
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25444452058
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note
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This unexpected chemoselectivity can be used for the selective functionalization of the amino group. The reductive animation of 36 with n-octanal to afford amino amide 43 (see below) is illustrative. (Diagram presented)
-
-
-
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