Iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl , efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols, with yields generally above 80%. Although the analogous N-H insertions are rapid at room temperature, the O-H insertion reactions are slower and required heating in refluxing methylene chloride for about 8 hours using 1.0 mol.% catalyst. Fe(TPP)Cl was also found to be effective for tandem N-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents to give piperazinones and morpholinones and related analogs such as quinoxalinones and benzoxazin-2-ones. This approach provides a new one-pot route for synthesizing these classes of heterocyclic compounds.

Palladium catalysts, generated from Pd(OAc)2 and 2 equiv of N,N-dialkylbenzimidazolium iodide, are effective for the alkoxycarbonylation of olefins in high yields (>90%). Alkoxycarbonylation of 1-hexene in dimethylacetamide is achieved within 24 h at 110 °C using 1 mol % catalyst, 1000 psi CO, and ethanol. Reactions can be prepared in air, without the need of an acid additive to produce ethyl 2-methylhexanoate and ethyl heptanoate in approximately a 2:1 ratio.

Aqueous Sonogashira coupling between lipophilic terminal alkynes and aryl bromides or iodides gave moderate to high yields at 40 C using readily available and inexpensive surfactants (2.0 w/v% in water) such as SDS and CTAB. The catalyst precursor was 2 mol% Pd(PPh 3 ) 2 Cl 2 , and included a 5 mol% Cu(I) co-catalyst for aryl iodide substrates. Aryl-bromide reagents were found to be inhibited by iodide and Cu(I). Studies under Cu(I)-free conditions reveal two competing pathways. A deprotonation pathway gives rise to the traditional Sonogashira product (3), while a carbopalladation pathway produces enyne, 5.The surfactant solution (SDS or CTAB) can be recycled up to three times for coupling between 1-octyne and 1-iodonapthalene in the presence of CuI before the yields decrease.