@article {CHEM:CHEM201504959,
	title = {Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex},
	journal = {Chemistry {\textendash} A European Journal},
	volume = {22},
	number = {12},
	year = {2016},
	pages = {4070{\textendash}4077},
	abstract = {Recently, esters have received much attention as transmetalation partners for cross-coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ-η2:η2-C6H6)] (dtbpe=1,2-bis(di-tert-butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2-carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl-S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross-coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η2-carbonyl complex, phenyl esters were found to predominantly undergo Caryl-O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2-naphthyl acetate was also found to undergo clean Caryl-O bond cleavage, and although stoichiometric cross-coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive.},
	keywords = {CROSS-COUPLING, ELIMINATION, NICKEL, P ligands, SULFUR},
	issn = {1521-3765},
	doi = {10.1002/chem.201504959},
	url = {http://dx.doi.org/10.1002/chem.201504959},
	author = {Desnoyer, Addison N. and Friese, Florian W. and Chiu, Weiling and Drover, Marcus W. and Patrick, Brian O. and Love, Jennifer A.}
}
@article {2092,
	title = {Mechanistic Studies on N-Acetylmuramic Acid 6-Phosphate Hydrolase (MurQ): An Etherase Involved in Peptidoglycan Recycling},
	journal = {Biochemistry},
	volume = {47},
	number = {44},
	year = {2008},
	note = {ISI Document Delivery No.: 366TUTimes Cited: 4Cited Reference Count: 37Hadi, Timin Dahl, Ulrike Mayer, Christoph Tanner, Martin E.},
	month = {Nov},
	pages = {11547-11558},
	type = {Article},
	abstract = {Peptidoglycan recycling is a process in which bacteria import cell wall degradation products and incorporate them back into either peptidoglycan biosynthesis or basic metabolic pathways. The enzyme MurQ is an N-acetylmuramic acid 6-phosphate (MurNAc 6-phosphate) hydrolase (or etherase) that hydrolyzes the lactyl side chain from MurNAc 6-phosphate and generates GlcNAc 6-phosphate. This study supports a mechanism involving the syn elimination of lactate to give an alpha,beta-unsaturated aldehyde with (E)-stereochemistry, followed by the syn addition of water to give product. The observation of both a kinetic isotope effect slowing the reaction of [2-H-2]MurNAc 6-phosphate and the incorporation of solvent-derived deuterium into C2 of the product indicates that the C2-H bond is cleaved during catalysis. The observation that the solvent-derived 180 isotope is incorporated into the C3 position of the product, but not the C1 position, provides evidence of the cleavage of the C3-O bond and argues against imine formation. The finding that 3-chloro-3-deoxy-GlcNAc 6-phosphate serves as an alternate substrate is also consistent with an elimination-addition mechanism. Upon extended incubations of MurQ with GlcNAc 6-phosphate, the alpha,beta-unsaturated aldehydic intermediate accumulates in solution, and H-1 NMR analysis indicates it exists as the ring-closed form of the (E)-alkene. A structural model is developed for the Escherichia coli MurQ and is compared to that of the structural homologue glucosamine-6-phosphate synthase. Putative active site acid/base residues are probed by mutagenesis, and Glu83 and Glu114 are found to be crucial for catalysis. The Glu83Ala mutant is essentially inactive as an etherase yet is capable of exchanging the C2 proton of substrate with solvent-derived deuterium. This suggests that Glu83 may function as the acidic residue that protonates the departing lactate.},
	keywords = {CATALYSIS, CELL-WALL, COLI GLUCOSAMINE-6-PHOSPHATE SYNTHASE, DERIVATIVES, ELIMINATION, ENOYL-COA HYDRATASE, ENVIRONMENT, ESCHERICHIA-COLI, INHIBITION, PHOSPHATE},
	isbn = {0006-2960},
	url = {<Go to ISI>://000260507100019},
	author = {Hadi, T. and Dahl, U. and Mayer, C. and Tanner, M. E.}
}
@article {1605,
	title = {Ortho-selective C-Hactivation of substituted benzenes effected by a tungsten alkylidene complex without substituent coordination},
	journal = {Organometallics},
	volume = {25},
	number = {17},
	year = {2006},
	note = {ISI Document Delivery No.: 070PZTimes Cited: 13Cited Reference Count: 36Tsang, Jenkins Y. K. Buschhaus, Miriam S. A. Legzdins, Peter Patrick, Brian O.},
	month = {Aug},
	pages = {4215-4225},
	type = {Article},
	abstract = {{Gentle thermolysis of the bis(neopentyl) complex Cp*W(NO)(CH2CMe3)(2) (1) at 70 degrees C in various substituted benzenes results in the loss of neopentane and the generation of the transient alkylidene complex Cp*W(NO)(=CHCMe3) (A), which subsequently effects single C-H bond activations of the benzenes. These activations exhibit a pronounced selectivity for the C-H linkages ortho to the benzene substituents. Thus, thermal reactions of 1 with C6H5X lead to the preferential formation of the corresponding Cp*W( NO)(CH2CMe3)(o-C6H4X) complexes, the ortho-selectivity, i. e.},
	keywords = {CLEAVAGE, CRYSTAL-STRUCTURE, ELIMINATION, H BONDS, IRIDIUM, MECHANISM, METAL-COMPLEXES, {ARYL},
	isbn = {0276-7333},
	url = {<Go to ISI>://000239536800028},
	author = {Tsang, J. Y. K. and Buschhaus, M. S. A. and Legzdins,Peter and Patrick, B. O.}
}
@article {814,
	title = {Enantioselective photochemical synthesis of a simple alkene via the solid state ionic chiral auxiliary approach},
	journal = {Journal of Organic Chemistry},
	volume = {69},
	number = {8},
	year = {2004},
	note = {ISI Document Delivery No.: 811DLTimes Cited: 7Cited Reference Count: 24},
	month = {Apr},
	pages = {2711-2718},
	type = {Article},
	abstract = {Irradiation of cis-bicyclo[4.3.0]non-8-ylacetophenone derivatives (1) in solution and the solid state yields cis-3a,4,5,6,7,7a-hexahydro-1H-indene (2) via a Norrish type II cleavage process. Asymmetric induction studies were conducted by providing the reactants with carboxylic acid substituents to which ionic chiral auxiliaries were attached through salt formation with optically pure amines. Irradiation of the salts (5 in total) in the crystalline state gave enantiomeric excesses of up to 44\%. Single-crystal X-ray diffraction studies were performed on ketone la as well as salts 1d and 1g, and on this basis, the structure-reactivity relationships involved are discussed.},
	keywords = {ELIMINATION, KETONES, PHOTOELIMINATION, REACTIVITY CORRELATIONS, RESOLUTION},
	isbn = {0022-3263},
	url = {<Go to ISI>://000220752500008},
	author = {Chen, S. and Patrick, B. O. and Scheffer, J. R.}
}
@article {4517,
	title = {Hydrocarbon C-H bond activation by a tungsten acetylene complex},
	journal = {Organometallics},
	volume = {18},
	number = {17},
	year = {1999},
	note = {ISI Document Delivery No.: 230KBTimes Cited: 13Cited Reference Count: 60},
	month = {Aug},
	pages = {3414-3428},
	type = {Article},
	abstract = {Thermal activation of Cp*W(NO)(eta(2)-CPhCH2)(CH2SiMe3) (1) in neat hydrocarbon solutions transiently generates Cp*W(NO)(eta(2)-PhC=CH) (A), which subsequently activates solvent C-H bonds. For example, the thermolysis of 1 in benzene solution generates quantitatively Cp*W(NO)(eta(2)-CPhCH2)(Ph) (2) The thermolysis of 1 in solutions of methyl-substituted arenes such as toluene or p-, m-, or o-xylene provides mixtures of aryl and benzyl vinyl complexes of the general formulas Cp*W(NO)(eta(2)-CPhCH2)(aryl), Cp*W(NO)(eta(2)-CPhCH2)(eta(1)-benzyl), or Cp*W(NO)(eta(2)-benzyl)(eta(1)-CPh=CH2). Similarly, the thermolysis of 1 in (Me3Si)(2)O affords Cp*W(NO)(eta(2)-CPhCH2)(CH2SiMe2OSiMe3) (10). Mechanistic and kinetic studies support the proposal that the formation of A from 1 by elimination of silane is the rate-controlling process in these reactions. Intra- and intermolecular selectivity studies reveal that the strongest C-H bond (yielding the stronger M-C bond) is the preferred site of reactivity, as expected. Dual C-H bond activation of aliphatic hydrocarbons occurs during the thermal activation ;of I in solutions of these substrates. Consequently, metallacycles of the form Cp*W(NO)(eta(2)-CH(eta(2)-Ph)CH2CH(R)CH2) [(11)R = Pr-n; (12)R = Bu-n; (13)R = Bu-t; and (14)R = OEt] result from the dehydrogenation of n-pentane, n-hexane, 2,2-dimethylbutane, and diethyl ether, respectively. This dual C-H activation process displays a selectivity for substrates that contain an ethyl substituent. Dual C-H bond activation of 2,3-dimethyl-2-butene in the presence of 1 under thermolysis conditions regioselectively affords Cp*W(NO)(eta(3)-endo-CH2C(Me)C(Me)CH2(eta(1)-CPhMe)) (15), Attempts to trap acetylene complex A with PNMe3 result in the formation of the metallacyclopropane complex Cp*W(NO)(CH2SiMe3)(eta(2)-CH2CPh(PMe3)) (16). All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of compounds 11, 15, and 16 have been established by X-ray diffraction methods.},
	keywords = {ELIMINATION, HYDROGEN-TRANSFER, ISOMERIZATION, LIGAND, METAL-COMPLEXES, MOLECULAR-STRUCTURE, ORGANIC-SYNTHESIS, ORGANOMETALLIC NITROSYL CHEMISTRY, OXIDATIVE ADDITION, REDUCTIVE, R{\textquoteright} =},
	isbn = {0276-7333},
	url = {<Go to ISI>://000082249400023},
	author = {Debad, D. and Legzdins,Peter and Lumb, S. A. and Rettig, S. J. and Batchelor, R. J. and Einstein, F. W. B.}
}
@article {7014,
	title = {PHOSPHINE COMPLEXES OF YTTRIUM, LANTHANUM, AND LUTETIUM - SYNTHESIS, THERMOLYSIS, AND FLUXIONAL BEHAVIOR OF THE HYDROCARBYL DERIVATIVES MR{\textquoteright}[N(SIME2CH2PME2)2]2 - X-RAY CRYSTAL-STRUCTURE OF Y[N(SIME2CHPME2)(SIME2CH2PME2)][N(SIME2CH2PME2)2]},
	journal = {Organometallics},
	volume = {10},
	number = {6},
	year = {1991},
	note = {ISI Document Delivery No.: FQ933Times Cited: 61Cited Reference Count: 41},
	month = {Jun},
	pages = {2026-2036},
	type = {Article},
	abstract = {{The preparation of phosphine complexes of the group 3 elements yttrium and lanthanum and the lanthanide metal lutetium is described. The reaction of 2 equiv of lithium salt of the mixed-donor ligand LiN(SiMe2CH2PR2)2 (R = Me, Ph, Pr(i)) with YCl3 or LuCl3 (R = Me only) leads to the formation of the bis(ligand) complexes MCl[N(SiMe2CH2PR2)2]2. The analogous lanthanum derivative requires the use of the corresponding potassium salt KN(SiMe2CH2PR2)2 (R = Me, Ph) with anhydrous LaCl3 to generate good yields of LaCl(N(SiMe2CH2PR2)2]2. Replacement of the remaining chloride with a hydrocarbyl ligand can be achieved for M = Y and Lu to generate MR[N(SiMe2CH2PMe2)2]2 (M = Y},
	keywords = {ALKYL, BOND ACTIVATION, CHEMISTRY, CRYSTALLOGRAPHIC CHARACTERIZATION, ELIMINATION, F-BLOCK METALS, HAFNIUM(IV), hydride, LIGAND, ORGANOLANTHANIDES},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1991FQ93300059},
	author = {Fryzuk,Michael D. and Haddad, T. S. and Rettig, S. J.}
}
