- High fidelity kinetic self-sorting in multi-component systems based on guests with multiple binding epitopes
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The molecular recognition platforms of natural systems often possess multiple binding epitopes, each of which has programmed functional consequences. We report the dynamic behavior of a system comprising CB[6], CB[7], and guests cyclohexanediammonium (1) and adamantanealkylammonium (2) that we refer to as a two-faced guest because it contains two distinct binding epitopes. We find that the presence of the two-faced guest-just as is observed for protein targeting in vivo-dictates the kinetic pathway that the system follows toward equilibrium. The influence of two-faced guest structure, cation concentration, cation identity, and individual rate and equilibrium constants on the behavior of the system was explored by a combination of experiment and simulation. Deconstruction of this system led to the discovery of an anomalous host-guest complex (CB[6]·1) whose dissociation rate constant (kout = 8.5 × 10-10 s-1) is ≈100-fold slower than the widely used avidin-biotin affinity pair. This result, in combination with the analysis of previous systems which uncovered extraordinarily tight binding events (Ka ≥ 1012 M-1), highlights the inherent potential of pursuing a systems approach toward supramolecular chemistry.
- Mukhopadhyay, Pritam,Zavalij, Peter Y.,Isaacs, Lyle
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- Ruthenium-catalyzed synthesis of secondary alkylamines: Selective alkylation with aliphatic amines
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The chemoselective N-alkylation of tert-alkylamines applying aliphatic amines is described for the first time. In the presence of the Shvo catalyst 1, tert-octylamine 4 and 1-adamantylamine 5 are alkylated using primary, secondary, and even tertiary amine
- Baehn, Sebastian,Hollmann, Dirk,Tillack, Annegret,Bellera, Matthias
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supporting information; experimental part
p. 2099 - 2103
(2009/08/14)
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