Ruthenium(II)-Catalyzed ortho C-O Bond formation of Substituted Aromatics with Oxygen Nucleophiles through C-H Bond Activation

The present review describes a ruthenium-catalyzed ortho C-O bond formation such as hydroxylation, benzoxylation and acetoxylation of substituted aromatics with oxygen nucleophiles via C-H bond activation. Various oxygen sources such as trifluoroacetic anhydride, aromatic carboxylic acids and acetic acid are used as nucleophiles in the reaction. Most of the reactions shown in the review mechanistically proceeds via a concerted deprotonation ortho metalation pathway. A fivemembered ruthenacycle intermediate was proposed in the reactions. These reactions provide an efficient route for the synthesis of ortho-hydroxy-, acetoxy- and benzoxy substituted aromatics in a highly regioselective manner in one pot.

[1]  M. Jeganmohan,et al.  ortho-Benzoxylation of N-alkyl benzamides with aromatic acids catalyzed by ruthenium(II) complex. , 2014, Chemistry.

[2]  L. Ackermann,et al.  C-H nitrogenation and oxygenation by ruthenium catalysis. , 2014, Chemical communications.

[3]  M. Jeganmohan,et al.  Ruthenium-catalyzed oxidative ortho-benzoxylation of acetanilides with aromatic acids. , 2013, Chemical communications.

[4]  Sunggak Kim,et al.  ortho-Acetoxylation of phosphonic and phosphoric monoacids via Pd(II) catalysis. , 2013, The Journal of organic chemistry.

[5]  L. Ackermann,et al.  Ortho- and para-selective ruthenium-catalyzed C(sp2)-H oxygenations of phenol derivatives. , 2013, Organic letters.

[6]  Xinglin Yang,et al.  Synthesis of 2-aminophenols and heterocycles by Ru-catalyzed C-H mono- and dihydroxylation. , 2013, Organic letters.

[7]  Gang Shan,et al.  Broadening the catalyst and reaction scope of regio- and chemoselective C-H oxygenation: a convenient and scalable approach to 2-acylphenols by intriguing Rh(II) and Ru(II) catalysis. , 2013, Organic & biomolecular chemistry.

[8]  Xinglin Yang,et al.  Pd-catalyzed C-H oxygenation with TFA/TFAA: expedient access to oxygen-containing heterocycles and late-stage drug modification. , 2012, Angewandte Chemie.

[9]  L. Ackermann,et al.  Ruthenium-catalyzed C-H bond oxygenations with weakly coordinating ketones. , 2012, Organic letters.

[10]  M. Sanford,et al.  Nitrate as a Redox Co-Catalyst for the Aerobic Pd-Catalyzed Oxidation of Unactivated sp(3)-C-H Bonds. , 2012, Chemical science.

[11]  C. Bruneau,et al.  Ruthenium(II)-catalyzed C-H bond activation and functionalization. , 2012, Chemical reviews.

[12]  L. Ackermann,et al.  Ruthenium-catalyzed oxidative C(sp2)-H bond hydroxylation: site-selective C-O bond formation on benzamides. , 2012, Organic letters.

[13]  C. Pan,et al.  Recent Advances in Transition-Metal-CatalyzedEsterification , 2012 .

[14]  C. Pan,et al.  Copper(II)-catalyzed ortho-functionalization of 2-arylpyridines with acyl chlorides. , 2011, Chemical communications.

[15]  L. Ackermann.  Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope. , 2011, Chemical reviews.

[16]  Yuhong Zhang,et al.  Palladium-catalyzed regioselective oxidative coupling of indoles and one-pot synthesis of acetoxylated biindolyls. , 2010, The Journal of organic chemistry.

[17]  Tingting Yuan,et al.  Palladium-catalyzed alkoxylation of N-methoxybenzamides via direct sp2 C-H bond activation. , 2010, The Journal of organic chemistry.

[18]  jin-quan yu,et al.  Pd(II)-catalyzed hydroxylation of arenes with 1 atm of O(2) or air. , 2009, Journal of the American Chemical Society.

[19]  Wanzhi Chen,et al.  Ortho-functionalization of 2-phenoxypyrimidines via palladium-catalyzed C-H bond activation. , 2009, The Journal of organic chemistry.

[20]  Mark E. Scott,et al.  Aryl-aryl bond formation by transition-metal-catalyzed direct arylation. , 2007, Chemical reviews.

[21]  jin-quan yu,et al.  Cu(II)-catalyzed functionalizations of aryl C-H bonds using O2 as an oxidant. , 2006, Journal of the American Chemical Society.

[22]  M. Sanford,et al.  Oxone as an inexpensive, safe, and environmentally benign oxidant for C-H bond oxygenation. , 2006, Organic letters.

[23]  Jue Liang,et al.  Pd-catalyzed stereoselective oxidation of methyl groups by inexpensive oxidants under mild conditions: a dual role for carboxylic anhydrides in catalytic C--H bond oxidation. , 2005, Angewandte Chemie.

[24]  M. Sanford,et al.  Palladium-catalyzed oxygenation of unactivated sp3 C-H bonds. , 2004, Journal of the American Chemical Society.

[25]  C. Sirlin,et al.  Ru-, Rh-, and Pd-catalyzed C-C bond formation involving C-H activation and addition on unsaturated substrates: reactions and mechanistic aspects. , 2002, Chemical reviews.

[26]  R. Crabtree,et al.  Pd(II) catalyzed acetoxylation of arenes with iodosyl acetate , 1996 .

[27]  P. Henry.  Palladium(II)-catalyzed aromatic substitution , 1971 .