Stereoselective self-sorting in the self-assembly of a Phe–Phe extended guanidiniocarbonyl pyrrole carboxylate zwitterion: formation of two diastereomeric dimers with significantly different stabilities

Abstract

The 'dipeptide extended' guanidiniocarbonyl pyrrole carboxylate zwitterion GCP-Phe-Phe 1 forms stable dimers in DMSO. However, dimerization is highly stereoselective. Only homochiral dimers are formed and the (L,L)·(L,L) dimer (K(dim) > 10(5) M(-1)) is significantly more stable by a factor of 10(3) than the diastereomeric (D,L)·(D,L) dimer (K(dim) = 120 M(-1)).

Making a Right or Left Choice: Chiral Self-Sorting as a Tool for the Formation of Discrete Complex Structures

“…The importance of interactions between side chains has also been confirmed by dimerization studies of a mixture of l - 29c and l - 29e that show a considerable sequence selectivity . Dimerization of dipeptide derivatives has also been reported for diphenylalanie equipped with a guanidiniocarbonyl pyrrole group, 30 , in DMSO (Figure b) . The dimerization proceeds by charge-assisted hydrogen bonds.…”

“…88 Dimerization of dipeptide derivatives has also been reported for diphenylalanie equipped with a guanidiniocarbonyl pyrrole group, 30, in DMSO (Figure 18b). 89 The dimerization proceeds by charge-assisted hydrogen bonds. All four stereoisomers of .…”

Chiral tether-mediated stabilization and helix-sense control of complementary metallo-double helices

“…Interestingly, the interstrand ligand exchange with racemic 1,3-diphosphine toward an optically-active Pt II -linked duplex composed of a chiral amidine strand diastereoselectively proceeded, finally producing totally homochiral trans -Pt II -bridged double helices via complete homochiral self-sorting. 30 The present findings will provide a versatile means for the rational design of functional double helix-based chiral materials for chiral recognition and also asymmetric catalysis 12 with high stability and selectivity. Further work along this line is currently ongoing in our laboratory.…”

Probing the self-assembly and anti-glioblastoma efficacy of a cinnamoyl-capped dipeptide hydrogelator

“…The obtained spectra were in agreement with previously published data. 38,39 Off-white gammy solid, 786 mg, stoichiometric yield-100%; 1 H NMR (500 MHz, D 6 -DMSO): δ 8.16 (d, J = 8.0 Hz, 1H), 7.29-7.12 (m, 11H), 4.44 (dt, J = 8.0, 6.9 Hz, 1H), 3.41 (dd, J = 8.4, 4.6 Hz, 1H), 2.94 (d, J = 6.9 Hz, 2H), 2.93-2.89 (m, 1H), 2.56 (dd, J = 13.5, 8.4 Hz, 1H), 1.33 (s, 9H); 13 Synthesis of Cin-L-F-L-FOtBu (6). Cinnamic acid (248 mg, 1.68 mmol), NaHCO 3 (294 mg, 3.49 mmol) and TBTU (673 mg, 2.09 mmol) were suspended in anhydrous DMF (4 mL) under N 2 atmosphere.…”