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Randell KD, Johnston BD, Green DF, et al. Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines. J Org Chem. 2000;65(1):220-6doi: 10.1021/jo991520j.
Randell, K. D., Johnston, B. D., Green, D. F., & Pinto, B. M. (2000). Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines. The Journal of organic chemistry, 65(1), 220-6. https://doi.org/10.1021/jo991520j
Randell, et al. "Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines." The Journal of organic chemistry vol. 65,1 (2000): 220-6. doi: https://doi.org/10.1021/jo991520j
Randell KD, Johnston BD, Green DF, Pinto BM. Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines. J Org Chem. 2000 Jan 14;65(1):220-6. doi: 10.1021/jo991520j. PMID: 10813919.
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J Org Chem. 2000 Jan 14;65(1):220-6. doi: 10.1021/jo991520j.

Is there a generalized reverse anomeric Effect? substituent and solvent effects on the configurational equilibria of neutral and protonated N-arylglucopyranosylamines and N-aryl-5-thioglucopyranosylamines.

The Journal of organic chemistry

Randell, Johnston, Green, Pinto

Affiliations

  1. Department of Chemistry, Simon Fraser University, Burnaby, British Columbia, Canada, V5A 1S6.

PMID: 10813919 DOI: 10.1021/jo991520j

Abstract

The effects of substitution and solvent on the configurational equilibria of neutral and protonated N-(4-Y-substituted-phenyl) peracetylated 5-thioglucopyranosylamines (Y = OMe, H, CF(3), NO(2)) 1-4 and N-(4-Y-substituted-phenyl) peracetylated glucopyranosylamines (Y = OMe, H, NO(2)) 9-11 are described. The configurational equilibria were determined by direct integration of the resonances of the individual isomers in the (1)H NMR spectra after equilibration of both alpha- and beta-isomers. The equilibrations of the neutral compounds 1-4 in CD(3)OD, CD(3)NO(2), and (CD(3))(2)CO were achieved by HgCl(2) catalysis and those of the neutral compounds 9-11 in CD(2)Cl(2) and CD(3)OD by triflic acid catalysis. The equilibrations of the protonated compounds in both the sulfur series (solvents, CD(3)OD, CD(3)NO(2), (CD(3))(2)CO, CDCl(3), and CD(2)Cl(2)) and oxygen series (solvents, CD(2)Cl(2) and CD(3)OD) were achieved with triflic acid. The substituent and solvent effects on the equilibria are discussed in terms of steric and electrostatic effects and orbital interactions associated with the endo-anomeric effect. A generalized reverse anomeric effect does not exist in neutral or protonated N-aryl-5-thioglucopyranosylamines and N-arylglucopyranosylamines. The anomeric effect ranges from 0.85 kcal mol(-)(1) in 2 to 1.54 kcal mol(-)(1) in 10. The compounds 1-4 and 9-11 show an enhanced endo-anomeric effect upon protonation, ranging from 1.73 kcal mol(-)(1) in 2 to 2.57 kcal mol(-)(1) in 10. We estimate the increase in the anomeric effect upon protonation of 10 to be approximately 1.0 kcal mol(-)(1). However, this effect is offset by steric effects due to the associated counterion which we estimate to be approximately 1.2 kcal mol(-)(1). The values of K(eq)(axial-equatorial) in protonated 1-4 increase in the order OMe < H < CF(3) < NO(2), in agreement with the dominance of steric effects (due to the counterion) over the endo-anomeric effect. The values of K(eq)(axial-equatorial) in protonated 9-11 show the trend OMe > H < NO(2) that is explained by the balance of the endo-anomeric effect and steric effects in the individual compounds. The trends in the values of the C(1)-H(1) coupling constants for 1-4 and the corresponding deacetylated compounds 5-8 as a function of substituent and alpha- or beta-configuration are discussed in terms of the Perlin effect and the interplay of the endo- and exo-anomeric effects.

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