Bioinspired Oxidations Catalyzed by Ruthenium Complexes

Modern Oxidation of Alcohols Using Environmentally Benign Oxidants

“…Ruthenium compounds are widely used as catalysts in organic synthesis [32,33] and have been extensively studied as catalysts for the aerobic oxidation of alcohols [34]. In 1978, Mares and coworkers [35] reported that RuCl 3 Á nH 2 O catalyzes the aerobic oxidation of secondary alcohols into the corresponding ketones, albeit in modest yields.…”

Ruthenium‐Catalyzed Oxidation for Organic Synthesis

“…The inactivation can be prevented by addition of CH 3 CN. Thus, various oxidations with RuO 4 were improved considerably by employing a solvent system consisting of CCl 4 -H 2 O-CH 3 CN [11c]. Typically, oxidative cleavage of (E)-5-decene (1) Modern Oxidation Methods.…”

“…Typically, oxidative cleavage of (E)-5-decene (1) Modern Oxidation Methods. Edited by Jan-Erling Bäckvall Copyright Ó 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32320-3 with the RuCl 3 /NaIO 4 system in a CCl 4 -H 2 O-CH 3 CN system gave pentanoic acid in 88% yield, while the same reaction in a conventional CCl 4 -H 2 O system gave pentanal (17%) along with 80% of recovered 1 (Eq. (7.1)).…”

“…Ruthenium complexes have great potential for catalytic oxidation reactions of various compounds [1][2][3][4][5][6][7][8][9][10]. The reactivity of ruthenium complexes can be controlled by its oxidation state and ligand.…”

Catalytic Enantioselective Oxidation of Alkanes and Alkenes Using (Salen)Manganese Complexes Bearing a Chiral Binaphthyl Strapping Unit

“…For this purpose, chiral metalloporphyrin complexes such as bridged iron-porphyrins bearing a chiral binaphthyl vaulted unit [2] and D 4 -symmetric chiral ruthenium porphyrins [3] and a concave type (salen)manganese complex 4 bearing a chiral environment [4] were designed and used for asymmetric hydroxylation of hydrocarbons. The (salen)manganese complexes 3[5] and 4 [6] are also known to be effective for the asymmetric epoxidation of alkenes (Figure 1).During the course of our study on the biomimetic oxidation of alkanes, [7,8] we found that enantioselective oxidation of symmetrical alkanes using the catalyst 3 proceeds to give the corresponding optically active ketones in up to 70% ee. [9] In order to aim at asymmetric hydroxylation of alkanes, we synthesized new bridged Mn(salen) complexes bearing a strapping unit (1 and 2).…”