Development of manganese (VI) oxidising agents soluble in organic solvents

Two manganate (VI) reagents have been prepared from permanganate salts that show excellent oxidizing properties in common organic solvants

Insights into the mechanism for gold catalysis: behaviour of gold(i) amide complexes in solution

We report the synthesis and activity of new mononuclear and dinuclear gold amide complexes . The dinuclear complexes and were characterised by single crystal X-ray analysis. We also report solution NMR and freezing point depression experiments to rationalise their behaviour in solution and question the de-ligation process invoked in gold catalysis

Gold amides as anticancer drugs: synthesis and activity studies

Modular gold amide chemotherapeutics: Access to modern chemotherapeutics with robust and flexible synthetic routes that are amenable to extensive customisation is a key requirement in drug synthesis and discovery. A class of chiral gold amide complexes featuring amino acid derived ligands is reported herein. They all exhibit in vitro cytotoxicity against two slow growing breast cancer cell lines with limited toxicity towards normal epithelial cells

Multicomponent cascade reactions: Sequential [1+4] and [2+3] cycloadditions for the generation of heterocyclic ring systems

A novel intermolecular nitrile oxide cycloaddition sequence has been developed for the formation of highly substituted heterocyclic rings. Reaction of trimethylsilyl cyanide with epoxides generates isonitriles which can react with nitroalkenes to form N-(isoxazolylidene)alkylamines. After fragmentation to nitrile oxides, the dipoles can undergo intermolecular 1,3-dipolar cycloadditions with electron deficient dipolarophiles to generate substituted isoxazolines in one synthetic operation

Investigation of the Reductive Cleavage of BINAP and Application to the Rapid Synthesis of Phospholes

A rapid and easy entry into λ³-phospholes and λ⁴-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental ³¹P resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism

Investigation of the Reductive Cleavage of BINAP and Application to the Rapid Synthesis of Phospholes

A rapid and easy entry into λ³-phospholes and λ⁴-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental ³¹P resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism

Investigation of the Reductive Cleavage of BINAP and Application to the Rapid Synthesis of Phospholes

A rapid and easy entry into λ³-phospholes and λ⁴-phosphole oxides derived from BINAP is reported herein featuring a variety of C and Si substituents and functional groups, as well the investigative work on the mechanistic pathway. DFT calculations using B3LYP functionals have been carried out to rationalize the mechanism. The observed experimental ³¹P resonance shifts were compared with the calculated shifts of the proposed intermediates after calibration of the shielding tensors. The calculations included the use of polarizable continuum models to take into account solvent effects and were found to be in excellent agreement, providing further evidence for the proposed mechanism