Dual water and organic solvent soluble 3-aryl-3-(trifluormethyl) diazirine-functionalized gold nanoparticles (AuNPs) were prepared through a place exchange reaction from triethylene glycol monomethyl ether (EG3-Me) capped AuNPs. These nanoparticles were fully characterized using 1H and 19F nuclear magnetic resonance (NMR) spectroscopy, transmission electron microscopy (TEM), thermogravimetric a...

The synthesis of simple imidazolium-based ligand precursors containing a 1,3-alkylidene-2,4,6-trimethylbenzene spacer was examined and different synthetic protocols were applied depending on the nature of the alkylidene arm. For a methylene arm, simple dications 5a,b.2CI were obtained directly. The higher homologue counterparts were conveniently prepared by general multistep routes following a ...

Phomactins are novel platelet activating factor (PAF) antagonists isolated from the culture of marine fungus Phoma sp.1 Members of the phomactin family share a unique [9.3.1] pentadecane ring system, and their biosynthetic pathway shares a branchpoint with the taxane family of natural products.1,2 Substantial synthetic efforts have been described in the literature toward the synthesis of severa...

In an effort to develop new tripodal N-heterocyclic carbene (NHC) ligands for small molecule activation, two new classes of tripodal NHC ligands TIME and TIMEN have been synthesized. The carbon-anchored tris(carbene) ligand system TIME (R = Me, t-Bu) forms bior polynuclear metal complexes. While the methyl derivative exclusively forms trinuclear 3:2 complexes [(TIME)2M3] 3+ with group 11 metal ...

An N -Heterocyclic carbene (NHC) catalyzed aza -benzoin reaction of benzothiazole-2-carboxaldehydes and -sulfonylimines is reported for the first time. The target benzothiazole-containing aminoketone products bearing different substituents substitution patterns can be obtained in good to excellent yields under mild conditions.

Research in the Herndon group focuses on the discovery of new organotransition metal-based processes for use in organic synthesis. Of specific interest are reactions that transform simple starting materials into complex products in a general, predictable, efficient, and stereoselective manner. Most of our present activity involves exploration of the coupling reaction between Fischer carbene com...

Au-catalyzed rearrangement of alkynes has attracted considerable attention in recent years. In particular, the Au-catalyzed rearrangement of propargyl acetate generates Au–carbene species through 1,2-acetoxy migration. The Au–carbene species thus generated undergoes a variety of transformations. Moreover, Au-catalyzed rearrangement of propargyl acetate to allene through 1,3-shift of the acetoxy...

Copolymerisation of carbenes and olefins (ethene), mediated by Rh-based catalyst precursors, is presented as a new, proof-of-concept methodology for the controlled synthesis of functional polymers. The reactions studied show that olefin-carbene polymerisation reactions provide a viable alternative to more traditional olefin polymerization techniques. Rh(III)-catalyst precursors, while active in...

We report the development of a multicatalytic, one-pot, asymmetric Michael/Stetter reaction between salicylaldehydes and electron-deficient alkynes. The cascade proceeds via amine-mediated Michael addition followed by an N-heterocyclic carbene-promoted intramolecular Stetter reaction. A variety of salicylaldehydes, doubly activated alkynes, and terminal, electrophilic allenes participate in a o...

The reaction of Ta(NMe2)5 with NHC·HBF4 (NHC = IMes and SIMes) leads to new carbene adducts of the mixed TaV amidofluoride, [(NHC)TaF3(NMe2)2]. On the contrary, the reaction of Ta(NMe2)5 with IMes·HCl gives a complex mixture, where [(aIMes)TaCl2(NMe2)3] is identified as one of the products. This is the first example of abnormal NHC coordination to an early transition metal.