Principles of Dynamic Covalent Chemistry

Configurational and Constitutional Dynamics of Enamine Molecular Switches

“…As demonstrated, the presence of pyridine and ester moieties adjacent to the enamine switch axle enabled tautomerization to form imine/iminium ion intermediates, thereby facilitating the switching process. This possibility of the imino‐form co‐existing with the enamine moiety also makes the switches susceptible to exchange with amines [18, 22] . Thus, the enamine‐amine exchange process would likely occur via the more studied transimination procedure (Scheme 9).…”

“…Four sets of enamine/amine pairs were subsequently employed to generate dynamic enamine systems containing 0, 1, or 2a mino acid-derived amines by double-entry-point analysis under the same conditions (Scheme 8), [18] where the resultsa re presented in Ta ble 1, entries [13][14][15][16][17][18][19]. The same equilibrium ratios, within the limits of the experimental error,w ere reached in each group, denoting the thermodynamic control in the dynamic enamine exchange process.…”

“…[21] As demonstrated, the presence of pyridine and ester moieties adjacentt ot he enamine switch axle enabled tautomerization to form imine/iminium ion intermediates,t herebyf acilitating the switching process.T his possibility of the imino-form co-existing with the enamine moiety also makes the switches susceptible to exchange with amines. [18,22] Thus, the enamineamine exchange process would likely occurv ia the more studied transimination procedure (Scheme 9). [23] The addition of primary amines to the enamine-iminet automeric mixture results in proton transfer in transition state TS1.T he results sug-Scheme8.Dynamic enamine systemg enerationf rom two-entry-point of four sets of substrates in CD 3 CN (0.5 mL) at 60 8C; relative kinetic rates (cf.…”

A tetrahedral molecular cage with a responsive vertex

“…A common characteristic of DCC reactions is the ability for these systems to ‘self-correct’ to a discrete product 8,16,53,63–65. In many systems employing alkyne metathesis, high molecular weight oligomeric/polymeric products are often formed at early reaction times and gradually convert to a single product 8,39.…”

Physical organic studies and dynamic covalent chemistry of picolyl heterocyclic amino aminals

“…Dynamic covalent chemistry is dened as a covalent bond that forms or breaks reversibly. [1][2][3][4][5][6][7] Several components undergo continuous exchange and reach an equilibrium in a stable distribution. [8][9][10][11] A dynamic covalent system can respond to external stimuli to achieve adaption, bringing dynamic diversity to allow variation and selection.…”