An Osmium(III)/Osmium(V) Redox Couple Generating Os-V(O)(OH) Center for cis-1,2-Dihydroxylation of Alkenes with H2O2: Os Complex with a Nitrogen-Based Tetradentate Ligand

作者：Sugimoto Hideki^*; Kitayama Kazuhiro; Mori Seiji; Itoh Shinobu

来源：Journal of the American Chemical Society, 2012, 134(46): 19270-19280.

DOI：10.1021/ja309566c

For the synthesis of the 1,2-diols, cis-1,2-dihydroxylation of alkenes catalyzed by osmium(VIII) tetroxide (OsO4) is a powerful method. However, OsO4 is quite toxic due to its highly volatile and sublimable nature. Thus, the development of alternative catalysts for cis-1,2-dihydroxylation of alkenes is highly challenging. Our approach involves the use of a nitrogen-based tetradentate ligand, tris(2-pyridylmethyl)amine (tpa), for an osmium center to develop a new osmium catalyst and hydrogen peroxide (H2O2) as a cheap and environmentally benign oxidant. The new Os tpa complex acts as a very efficient turnover catalyst for syn-selective dihydroxylation of various alkenes (turnover number similar to 4000) in aqueous media, and H2O2 oxidant is formally incorporated into the products quantitatively (100% atom efficiency). The reaction intermediates involved in the catalytic cycle have been isolated and characterized crystallographically as [Os-III(OH)(H2O)(tpa)](2+) and [Os-V(O)(OH)(tpa)](2+) complexes. The observed syn-selectivity, structural characteristics of the intermediates, and kinetic studies have suggested a concerted [3 + 2]-cycloacldition mechanism between [Os-V(O)(OH)(tpa)](2+) and alkenes, which is strongly supported by DFT calculations.

• 出版日期2012-11-21