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Volumn 70, Issue 20, 2005, Pages 7829-7840

Regio- and stereoselective synthesis of aminoinositols and 1,2-diaminoinositols from conduritol B epoxide

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; AMINES; ISOMERIZATION; ORGANIC COMPOUNDS; SYNTHESIS (CHEMICAL);

EID: 25444489938     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo050521a     Document Type: Article
Times cited : (42)

References (73)
  • 1
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    • (1997) Carbohydrates in Drug Design , pp. 433-469
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    • (Ajinomoto Co. Inc.). Japanese Patent Application JP 86-161529, 1988
    • Suami, T.; Shiio, T.; Kazuo, O.; Kunisuke, I. (Ajinomoto Co. Inc.). Japanese Patent Application JP 86-161529, 1988.
    • Suami, T.1    Shiio, T.2    Kazuo, O.3    Kunisuke, I.4
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    • (Ajinomoto Co. Inc.). Japanese Patent Application JP85-127551, 1986
    • Suami, T.; Takeshi, S. (Ajinomoto Co. Inc.). Japanese Patent Application JP85-127551, 1986.
    • Suami, T.1    Takeshi, S.2
  • 29
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    • Reference 7
    • For trans-1,2-diaminocyclitols from N-tosyl or N-acyl aziridines see: (a) Reference 7.
  • 34
    • 0037534204 scopus 로고    scopus 로고
    • For general synthesis of trans-1,2-diaminocyclohexane derivatives from N-substituted aziridinecyclohexane derivatives, see: (f) Watson, I. D.; Yudin, A. K. J. Org. Chem. 2003, 68, 5160-5167.
    • (2003) J. Org. Chem. , vol.68 , pp. 5160-5167
    • Watson, I.D.1    Yudin, A.K.2
  • 41
    • 0034602189 scopus 로고    scopus 로고
    • 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.
    • (2000) Carbohydr. Res. , vol.329 , pp. 301-308
    • Falshaw, A.1    Hart, J.B.2    Tyler, P.C.3
  • 49
    • 0028032620 scopus 로고
    • and references therein
    • For the use of chelation-controlled aminolysis and azidolysis of 1,2-epoxycyclohexanes bearing remote polar groups, see Calvani, F.; Crotti, P.; Gardelli, C.; Pineschi, M. Tetrahedron 1994, 50, 12999-13022 and references therein.
    • (1994) Tetrahedron , vol.50 , pp. 12999-13022
    • Calvani, F.1    Crotti, P.2    Gardelli, C.3    Pineschi, M.4
  • 51
    • 25444504726 scopus 로고    scopus 로고
    • note
    • In all cases, the major conformation is assumed to be that imposed by the "all-equatorial" disposition of the OBn groups.
  • 56
    • 25444485358 scopus 로고    scopus 로고
    • 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).
  • 57
  • 58
    • 0032440268 scopus 로고    scopus 로고
    • (b) Riley, A. M.; Jenkins, D. J.; Potter, B. V. L. Carbohydr. Res. 1998, 314, 277-281. Although we have never observed the corresponding formate ester, its formation and in situ hydrolysis along the reaction course cannot be ruled out.
    • (1998) Carbohydr. Res. , vol.314 , pp. 277-281
    • Riley, A.M.1    Jenkins, D.J.2    Potter, B.V.L.3
  • 60
    • 25444458763 scopus 로고    scopus 로고
    • note
    • 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
  • 62
    • 0027370483 scopus 로고
    • 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.
    • (1993) J. Org. Chem. , vol.58 , pp. 5271-5273
    • Guidot, J.P.1    Legall, T.2
  • 66
    • 25444486314 scopus 로고    scopus 로고
    • note
    • 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).
  • 67
    • 25444474641 scopus 로고    scopus 로고
    • note
    • 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.
  • 69
    • 25444522547 scopus 로고    scopus 로고
    • note
    • 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).
  • 71
    • 0742269730 scopus 로고    scopus 로고
    • 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).
    • (2004) Tetrahedron Lett. , vol.45 , pp. 1223-1226
    • Surfraz, M.B.U.1    Akhtar, M.2    Allemann, R.K.3
  • 73
    • 25444452058 scopus 로고    scopus 로고
    • note
    • 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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