Photoinduced twisted intramolecular charge transfer (TICT) of meso-(4-dimethylamino)phenylamino subporphyrin and meso-(4-nitro)phenylamino subporphyrin has been revealed by steady-state and time-resolved absorption/fluorescence experiments and quantum calculations. Subporphyrins and undergo molecular twisting at the Cmeso-N bond and the N-Cipso bond, respectively, to trigger intramolecular char...

2D 1H-15N HMBC NMR acquired at natural abundance and DMSO titration monitored by 1D 1H NMR verified the existence of an intramolecular hydrogen bond that was designed to mimic the pyrimidinone ring of a class of kinase inhibitors. A scalar coupling across the hydrogen bond was detected in organic and aqueous solvent, suggesting a simple and general approach for testing the propensity of intramo...

The intermolecular thiol-ene reaction is emerging as a highly efficient; free-radical mediated "click" process with diverse applications in biofunctionalisation and materials science. The related intramolecular thiol-ene reactions offer significant potential for the preparation of a wide range of sulphur containing heterocycles including synthetic therapeutics such as cyclic peptides and thiosu...

step in the biosynthesis of 1 is the formation of the precursor, 2-deoxy-scy//0-inosose (2), from D-glucose (3) via the intramolecular C-C bond formation between C-l and C-6.li2) The transformation of 3 into 2 was proposed by us to involve a multi-step mechanismas shownin Scheme1, the chemistry of which was suggested to be similar to the dehydroquinate synthase in the shikimate pathway,3'4* and...

Detailed analysis of calculated data from an experimental/computational study of intramolecular furan Diels-Alder reactions has led to the unusual discovery that the mean contraction of the newly forming C-C σ-bonds from the transition state to the product shows a linear correlation with both reaction Gibbs free energies and reverse energy barriers. There is evidence for a similar correlation i...

We study a model for water with a tunable intramolecular interaction J(sigma), using mean-field theory and off-lattice Monte Carlo simulations. For all J(sigma)> or =0, the model displays a temperature of maximum density. For a finite intramolecular interaction J(sigma)>0, our calculations support the presence of a liquid-liquid phase transition with a possible liquid-liquid critical point for ...

By excite-and-probe spectroscopy with subpicosecond time resolution, we have measured the intramolecular electronic energy transfer in bichromophoric coumarins linked by a flexible polymethylene chain. The transfer proceeds on a time scale between 1 and 20 ps depending on the polymethylene chain length. The results can be well described by a dipole-dipole interaction model that takes into accou...

The effective formation of 1-azabicyclo[1.1.0]butane (2) by treatment of 2,3-dibromopropylamine hydrobromide (1) with n-BuLi could be understood considering a rational reaction pathway via both transition states 10 and 19 based on the intramolecular Br...Li(+) coordination. A similar cyclization pathway starting from N-benzyl-3-bromopropylamine hydrochloride (17) to afford N-benzylazetidine (18...

By finding that intramolecular properties and smearing dynamics of a solvation shell exhibit the anomalous order crossing Widom line, we demonstrated supercritical fluid is mixture liquid gas possessing heterogeneity.

A formal, metal-free, [2 + 2 + 2] cycloaddition strategy is described based on a cascade of two pericyclic processes. The first step involves an intramolecular propargylic ene reaction of a 1,6-diyne to generate a vinylallene, which then reacts in an inter- or intramolecular Diels-Alder reaction with an alkenyl or alkynyl dienophile. Reactions involving unsymmetrical alkenyl and alkynyl dienoph...