Efficient conversion of ketones into kinetic enol phosphates under mild and accessible conditions has been realised using the developed methods with di-tert-butylmagnesium and bismesitylmagnesium. Optimisation of the quench protocol resulted in high yields of enol phosphates from a range of cyclohexanones and aryl methyl ketones, with tolerance of a range of additional functional units.

The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.

The rhodium(III)-catalyzed mild and site-selective C-H allylation of enol carbamates with 4-vinyl-1,3-dioxolan-2-one and allylic carbonates affords allylic alcohols and terminal allylated products, respectively. The assistance of the carbamoyl directing group provides a straightforward preparation of biologically and synthetically important allylated enol carbamates.

Relative tautomerization energies, dipole moments and polarizabilities for the tautomers of (R)-4-amino-1,2oxazolidin-3-one (Cycloserine) was studied by quantum-chemical calculations, using the HF and DFT(B3LYP) level of theory with the 6-311++G(d,p) basis set in the gas phase and different solvents using SCRF model, with full geometry optimization. Entropies, enthalpies, Gibbs free energies an...

The additive-free tetrazine/enol ether click reaction was performed in ultra-high vacuum (UHV) with an enol group covalently linked to a silicon surface: Dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate molecules were coupled the of functionalized cyclooctyne which adsorbed on (001) surface via strained triple bond cyclooctyne. observed at substrate temperature 380 K by means X-ray photoelectron sp...

Density functional theory (DFT) (Becke3LYP functional and the D95 basis set) was used to study the influence of substitution on the dimethyldioxirane epoxidation reaction of six- and seven-membered cyclic enol ethers. In agreement with our previously reported experimental results, the calculations predict that substitution on the cyclic enol ether influences the level of diastereoselectivity. A...

The binding of an excess electron to HCN and HNC was studied at the coupled cluster level of theory with single, double, and noniterative triple excitations and with extended basis sets to accommodate the loosely bound excess electron. The HCN molecule, with a dipole moment of 3.05 Debye, binds an electron by 10 cm, whereas the HNC tautomer possesses a similar dipole moment ~3.08 Debye! and bin...

A metal-free and formal [2 + 2 + 2] cycloaddition of triynes has emerged recently as a novel methodology for the synthesis of fused tricyclic compounds via an intramolecular cascade propargylic ene reaction, Diels-Alder cycloaddition and tautomerization. DFT calculations on three model systems reveal that the ene reaction with low distortion energy makes the metal-free strategy feasible and, as...

Tautomerization is a fundamental chemical reaction which involves the relocation of proton in reactants. Studying optical properties tautomeric species challenging because ensemble averaging. Many molecules, such as porphines, porphycenes, or phenanthroperylene quinones, exhibit reorientation transition dipole moment (TDM) during tautomerization, can be directly observed single-molecule experim...