The Suzuki-Miyaura coupling reaction represents one of the most important synthetic transformations developed in the 20th century. However, the use of toxic organic solvents remains a scientific challenge and an aspect of economical and ecological relevance, and benign water as a reaction medium was found to be highly effective to overcome some of these issues. In the present manuscript, we described Suzuki-Miyaura coupling reactions in neat water, without using any phase transfer reagent. Notably, this protocol also works with ultra-low loading of catalyst with high turnover numbers and also able to couple challenging substrates like aryl chlorides.

The palladium(0) complexes of (E,E,E)‐1,6,11‐tris(arenesulfonyl)‐1,6,11‐triazacyclopentadeca‐3,8,13‐trienes deliver palladium to phosphanes with the generation of high concentrations of catalytically active species such as Pd(PPh3)2. After oxidation of the phosphanes, the palladium is reincorporated into the macrocycle, thus avoiding agglomeration and precipitation. These conclusions were reached by 31P NMR, 19F NMR, and electrospray ionization mass spectrometry studies of telomerization and Tsuji−Trost reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The Pd(OCOCF3)2/[(HOCH2CH2NHCOCH2)2NCH2]2-catalyzed oxidation of o-allylphenol with H2O2 in water/methanol affords a syn and anti mixture of 2-(1,2-dihydroxypropyl)phenol and 2-(2-hydroxy-1-methoxypropyl)phenol. Mechanistic experiments and ESI-MS studies support a pathway wherein isomerization of the C=C bond followed by its epoxidation and oxirane opening led to the products. Recycling of the catalytic system led to gradual lost of activity.

Allylic substitution of PhCH(OAc)CHdCHPh by CH 2 (COMe) 2 in a basic MeOH/H 2 O mixture could be achieved in the absence of a palladium catalyst and lead to a mixture of PhCH(CH(COMe) 2 )CHdCHPh and PhCH(OMe)CHdCHPh in 40% and 55% yields, respectively. The process is induced by water, and nucleophilic attack addition occurred on a stabilized carbocation as the intermediate. Addition of a catalytic amount of PdCl 2 (CH 3 CN) 2 did not accelerate the reaction but improved the selectivity, and PhCH(CH(COMe) 2 )CHdCHPh was then obtained in 92% yield while PhCH(OMe)-CHdCHPh was observed in trace amounts. An ESI-MS analysis of the reaction mixture led us to assume that a palladium acetylacetonate complex is involved in the formation of PhCH(CH(COMe) 2 )CHdCHPh.