Supporting Figures

Files in this Data Supplement:

Supporting Figure 8
Supporting Figure 9
Supporting Figure 10
Supporting Figure 11
Supporting Figure 12
Supporting Figure 13
Supporting Figure 14
Supporting Figure 15
Supporting Figure 16
Supporting Figure 17
Supporting Figure 18
Supporting Figure 19
Supporting Figure 20
Supporting Figure 21
Supporting Figure 22
Supporting Figure 23
Supporting Figure 24




Supporting Figure 8

Fig. 8. Upfield region of the ¹H–¹H COSY spectrum of the introverted heptyl ester C₇H₁₅1 in mesitylene-d₁₂ at 273 K.

Supporting Figure 9

Fig. 9. Downfield region of the ¹H NMR spectra of selected introverted ester cavitands in mesitylene-d₁₂. The spectra of Me1, Et1, Pr1, and Bu1 were acquired at 300 K; the others were acquired at 273 K.

Supporting Figure 10

Fig. 10. The introverted sec-butyl ester s-Bu1 is formed in 20% diastereomeric excess (d.e.) (spectrum A), which can be separated by HPLC to give the major (B) and minor (C) diastereomers. The control ester s-Bu2 is formed in 5% d.e. (spectra not shown).

Supporting Figure 11

Fig. 11. Methyl ester Me1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K): MS (MALDI–FTMS) calcd. for C₉₁H₉₄N₈O₁₇Na⁺ 1593.6629, found 1593.6669.

Supporting Figure 12

Fig. 12. Ethyl Ester Et1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K): MS (MALDI–FTMS) calcd. for C₉₂H₉₇N₈O₁₇⁺ 1585.6966, found 1585.6977.

Supporting Figure 13

Fig. 13. Propyl Ester Pr1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K): MS (MALDI–FTMS) calcd. for C₉₃H₉₉N₈O₁₇⁺ 1599.7122, found 1599.7184.

Supporting Figure 14

Fig. 14. Butyl Ester Bu1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K): MS (ESI–TOF) calcd. for C₉₄H₁₀₁N₈O₁₇⁺ 1613.7279, found 1613.7276.

Supporting Figure 15

Fig. 15. sec-Butyl Ester s-Bu1 mixture of diastereomers. ¹H NMR (mesitylene-d₁₂, 300 MHz, 298 K): MS (ESI–TOF) calcd. for C₉₄H₁₀₁N₈O₁₇⁺ 1613.7279, found 1613.7290.

Supporting Figure 16

Fig. 16. sec-Butyl Ester s-Bu1 Major Diastereomer. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K):

Supporting Figure 17

Fig. 17. sec-Butyl Ester s-Bu1 Minor Diastereomer. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K).

Supporting Figure 18

Fig. 18. Heptyl Ester C₇H₁₅1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 273 K): MS (ESI–TOF) calcd. for C₉₇H₁₀₇N₈O₁₇⁺ 1655.7748, found 1655.7707.

Supporting Figure 19

Fig. 19. Octyl Ester C₈H₁₇1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 273 K): MS (ESI–TOF) calcd. for C₉₈H₁₀₉N₈O₁₇⁺ 1669.7905, found 1669.7944.

Supporting Figure 20

Fig. 20. Nonyl Ester C₉H₁₉1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 273 K): MS (ESI–TOF) calcd. for C₉₉H₁₁₁N₈O₁₇⁺ 1683.8061, found 1683.8050.

Supporting Figure 21

Fig. 21. Decyl Ester C₁₀H₂₁1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 278 K): MS (ESI–TOF) calcd. for C₁₀₀H₁₁₃N₈O₁₇⁺ 1697.8218, found 1697.8221.

Supporting Figure 22

Fig. 22. Benzyl Ester Bn1. ¹H NMR (mesitylene-d₁₂, 600 MHz, 300 K): MS (ESI–TOF) calcd. for C₉₇H₉₉N₈O₁₇⁺ 1647.7122, found 1647.7152.

Supporting Figure 23

Fig. 23. Control Benzyl Ester Bn2. Model acid H2¹ (105 mg, 0.18 mmol) was dissolved in CH₂Cl₂ (5 ml). A freshly prepared solution of phenyldiazomethane in hexanes was added until the yellow color persisted. Rotary evaporation followed by flash chromatography [EtOAc:hexanes (1:4)] yielded the product as a clear oil (42 mg, 36% yield).¹H NMR (CDCl₃, 300 MHz, 298K) d 7.78 (s, 1H), 7.28 (m, 1H), 7.26 (m, 2H), 7.15 (s, 1H), 7.11 (m, 2H), 4.28 (d, J = 12 Hz, 1H, Bn methylene), 3.96 (m, 4H), 3.77 (d, J = 12 Hz, 1H, Bn methylene), 2.84 (d, J = 14 Hz, 1H), 2.81 (d, J = 14 Hz, 1H), 2.24 (d, J = 13 Hz, 1H), 1.80 (m, 4H), 1.60 (m, 3H), 1.44 (m, 4H), 1.41 (s, 3H), 1.28 (m, 19H), 1.15 (s, 3H), 0.88 (m, 6H) ppm). MS (ESI–TOF) calcd. for C₄₁H₅₉N₂O₅⁺ 659.4418, found 659.4419. ¹H NMR (CDCl₃, 300 MHz, 298 K):

Supporting Figure 24

Fig. 24. Control sec-butyl esters s-Bu1. Model acid H2 (5 mg, 8.5 mmol) was dissolved in CH₂Cl₂ (1 ml). A freshly prepared solution of diazo-sec-butane was added until the orange–red color persisted. Rotary evaporation gave the products: a mixture of diastereomers in 5% d.e. ¹H NMR (mesitylene-d₁₂, 300 MHz, 298 K):

1. Wash, P. L., Renslo, A. R. & Rebek, J., Jr. (2001) Angew. Chem. Int. Ed. 40, 1221–1222.