Versatile and practical macrocyclic reagent with multiple hydrogen-bonding sites for chiral discrimination in NMR

Tadashi Ema, Daisuke Tanida, Takashi Sakai

Research output: Contribution to journalArticle

139 Citations (Scopus)

Abstract

Bifunctional macrocycles 1-4 and diamide 5 were designed and synthesized. NMR studies demonstrated that, among them, receptor 1 functions as the best chiral solvating agent (shift reagent), which is effective for a wide range of chiral compounds having a carboxylic acid, oxazolidinone, carbonate, lactone, alcohol, sulfoxide, sulfoximine, sulfinamide, isocyanate, or epoxide functionality. The addition of only 5 mol % (69 μg, 0.15 mM) of 1 splits the enantiomeric signals of sulfoxide 13. The excellent performance of 1 as a chiral solvating agent, such as versatility, signal sharpness, high splitting ability, high sensitivity, wide detection window, and synthetic accessibility, is reported. NMR studies revealed that the principal binding site of 1 is the two amide NH groups of the lower segment and that the additional binding site is the pyridyl nitrogen. The V-shaped arrangement of the two 2,6-diacylaminopyridine moieties as constructed in 1 was found to be much more effective for binding a variety of compounds than the parallel alignment of the two binding motifs as constructed in 4. The NO2 group in 1 enhanced not only the binding ability but also the degree of enantioselectivity. Unexpectedly, the comparisons between 1 and 3 enabled us to find the importance of the relative orientation of the binaphthyl moiety; the orthogonal disposition of the binaphthyl moiety in 1 most effectively brings about the differential ring-current effect on the chiral guest molecule bound, which leads to the high degree of chiral discrimination in NMR.

Original languageEnglish
Pages (from-to)10591-10596
Number of pages6
JournalJournal of the American Chemical Society
Volume129
Issue number34
DOIs
Publication statusPublished - Aug 29 2007

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sulfoxide
Hydrogen Bonding
Hydrogen bonds
Binding Sites
Nuclear magnetic resonance
Binding sites
Diamide
Oxazolidinones
Isocyanates
Carbonates
Epoxy Compounds
Lactones
Carboxylic Acids
Amides
Nitrogen
Enantioselectivity
Alcohols
Carboxylic acids
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Versatile and practical macrocyclic reagent with multiple hydrogen-bonding sites for chiral discrimination in NMR. / Ema, Tadashi; Tanida, Daisuke; Sakai, Takashi.

In: Journal of the American Chemical Society, Vol. 129, No. 34, 29.08.2007, p. 10591-10596.

Research output: Contribution to journalArticle

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