Oxidation of Olefins by Palladium(II). 16. A New Palladium(II)-Catalyzed Asymmetric Chlorohydrin Synthesis

2473's picture
Journal Title, Volume, Page: 
Organometallics, 17 (23), pp 5184–5189
Year of Publication: 
Hamed, O.
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Henry, P.M
Preferred Abstract (Original): 
Abstract Image

Previous studies showed that palladium(II) catalysts containing a pyridine ligand give mainly ethylene chlorohydrin as a product of the oxidation of ethene in the presence of CuCl2 at [Cl-] = 0.2 M. Under the same conditions PdCl42- produced only ethanal. The replacement of pyridine by a chiral monoamine gave a catalyst which oxidized propene and methyl vinyl ketone to optically active chlorohydrins. However, the optical yields were low, with ee's of only 8−12%. The use of chelating diphosphines would be expected to greatly improve optical yields. However, the neutral catalysts containing diphosphine ligands were insoluble in the mixed H2O−THF (4/1) reaction media. The chiral ligands (2S,4S)-bis(diphenylphosphino)pentane ((S,S)-BDPP), (2S,3S)-bis(diphenylphosphino)butane ((S,S)-Chiraphos), and (R)−(+)-2,2‘-bis(di-p-tolylphosphino)-1,1‘-binaphthyl ((R)-Tol-BINAP) were sulfonated to give water-soluble catalysts. These catalysts gave poor to modest ee's (28−76%) in the oxidation of propene, methyl vinyl ketone, and allyl phenyl ether. In H2O−THF mixed solvents richer in THF (1/2 H2O/THF), unsulfonated (R)-Tol-BINAP is soluble to some extent. Oxidation of the above olefinic substrates with this system gave the corresponding chlorohydrins with slightly higher enantioselectivities than with the sulfonated catalysts. The absolute configuration of the chlorohydrin from propene with the (R)-Tol-BINAP catalyst was R. The oxidation of 2,3-dihydrofuran gave chlorohydrins with the E conformation. These two stereochemical results are consistent with anti addition to the most stable π-complex followed by a Pd(II)−carbon bond-breaking step which places a chloride from the coordination sphere of Pd(II) on the carbon which is leaving.