Abstract
Alkanes adopt extended conformations in solution that minimize steric interactions and maximize surface area. Folding can reduce the amount of hydrophobic surface exposed to solvent, but sterically unfavorable gauche interactions result. However, we found that the alkyl chains of two common surfactants in aqueous solution adopt helical conformations when bound within a synthetic receptor. The receptor recognizes the helical alkane better than the extended conformation, even though 2 to 3 kilocalories per mole of strain is introduced. The proper filling of space and burial of hydrophobic surface drive the molecular recognition between the receptor and the coiled alkane.
References
25
Referenced
213
-
P. Soncini, S. Bonsignore, E. Dalcanale, F. Ugozzoli, J. Org. Chem.57, 4608 (1992).
(
10.1021/jo00043a015) / J. Org. Chem. (1992) -
T. Haino, D. M. Rudkevich, A. Shivanyuk, K. Rissanen, J. Rebek Jr., Chem. Eur. J.6, 3797 (2000).
(
10.1002/1521-3765(20001016)6:20<3797::AID-CHEM3797>3.0.CO;2-1) / Chem. Eur. J. (2000) -
A. Casnati, F. Sansone, R. Ungaro, Acc. Chem. Res.36, 246 (2003).
(
10.1021/ar0200798) / Acc. Chem. Res. (2003) -
L. Trembleau, F. Hof, E. Ullrich, J. Rebek Jr., Angew. Chem. Int. Ed.42, 3150 (2003).
(
10.1002/anie.200351174) / Angew. Chem. Int. Ed. (2003) - J. L. Atwood, A. Szumna, Chem. Commun. 8, 940 (2003). / Chem. Commun (2003)
- J. L. Atwood, A. Szumna, J. Am. Chem. Soc.124, 16046 (2002). / J. Am. Chem. Soc. (2002)
-
J.-M. Lehnet al., Supramol. Chem.5, 97 (1995).
(
10.1080/10610279508029480) / Supramol. Chem. (1995) -
J. L. Atwood, L. J. Barbour, P. C. Junk, W. Orr, Supramol. Chem.5, 105 (1995).
(
10.1080/10610279508029481) / Supramol. Chem. (1995) -
H.-J. Schneider, U. Schneider, J. Org. Chem.52, 1613 (1987).
(
10.1021/jo00384a046) / J. Org. Chem. (1987) - K. Murayama, K. Aoki, Chem. Commun.119 (1997). / Chem. Commun.
10.1021/bi00438a031-
N. J. Turro, A. Yekta, J. Am. Chem. Soc.100, 5951 (1978).
(
10.1021/ja00486a062) / J. Am. Chem. Soc. (1978) -
K. Goodling, K. Johnson, L. Lefkowitz, B. W. Williams, J. Chem. Educ.71, A8 (1994).
(
10.1021/ed071pA8) / J. Chem. Educ. (1994) -
J. Van Stam, S. Depaemelaere, F. C. De Schryver, J. Chem. Educ.75, 93 (1998).
(
10.1021/ed075p93) / J. Chem. Educ. (1998) -
E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. Int. Ed.42, 1210 (2003).
(
10.1002/anie.200390319) / Angew. Chem. Int. Ed. (2003) -
B. R. Peterson, P. Wallimann, D. R. Carcanague, F. Diederich, Tetrahedron51, 401 (1995).
(
10.1016/0040-4020(94)00905-A) / Tetrahedron (1995) - M. Nishio M. Hirota Y. Umezawa The CH/π Interaction (Wiley New York 1998).
-
W. Blokzijl, J. B. F. N. Engberts, Angew. Chem. Int. Ed. Engl.32, 1545 (1993).
(
10.1002/anie.199315451) / Angew. Chem. Int. Ed. Engl. (1993) -
M. V. Rekharsky, Y. Inoue, Chem. Rev.98, 1875 (1998).
(
10.1021/cr970015o) / Chem. Rev. (1998) -
S. Mecozzi, J. Rebek Jr., Chem. Eur. J.4, 1016 (1998).
(
10.1002/(SICI)1521-3765(19980615)4:6<1016::AID-CHEM1016>3.0.CO;2-B) / Chem. Eur. J. (1998) - E. L. Eliel, S. H. Wilen, Stereochemistry of Organic Compounds (Wiley Interscience, New York, 1994), p. 600. / Stereochemistry of Organic Compounds (1994)
-
D. M. Rudkevich, G. Hilmersson, J. Rebek Jr., J. Am. Chem. Soc.120, 12216 (1998).
(
10.1021/ja982970g) / J. Am. Chem. Soc. (1998) -
F. Mohamadiet al., J. Comput. Chem.11, 440 (1990).
(
10.1002/jcc.540110405) / J. Comput. Chem. (1990) -
D. Q. McDonald, W. C. Still, Tetrahedron Lett. 33, 7743 (1992).
(
10.1016/0040-4039(93)88034-G) / Tetrahedron Lett (1992) - We thank the Skaggs Institute for Research and NIH (GM 27932) for financial support and F. Hof for valuable advice. L.T. is a Skaggs Postdoctoral Fellow.
@article{Trembleau_2003, title={Helical Conformation of Alkanes in a Hydrophobic Cavitand}, volume={301}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1086644}, DOI={10.1126/science.1086644}, number={5637}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Trembleau, Laurent and Rebek, Julius}, year={2003}, month=aug, pages={1219–1220} }