Cobalt , trifluoromethanesulfonate

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

Beccalli et al. reported a new synthesis of staurosporinone (293) from 3-cyano-3-(lH-indol-3-yl)-2-oxo propionic acid ethyl ester (1464) (790). The reaction of 1464 with ethyl chlorocarbonate and triethylamine afforded the compound 1465, which, on treatment with dimethylamine, led to the corresponding hydroxy derivative 1466. The triflate 1467 was prepared from 1466 by reaction with trifluoromethanesulfonic anhydride (Tf20) in the presence of ethyldiisopropylamine. The palladium(O)-catalyzed cross-coupling of the triflate 1467 with the 3-(tributylstannyl)indole 1468 afforded the vinylindole 1469 in 89% yield. Deprotection of both nitrogen atoms with sodium ethoxide in ethanol to 1470, followed by photocyclization in the presence of iodine as the oxidizing agent provided the indolocarbazole 1471. Finally, reductive cyclization of 1471 with sodium borohydride-cobaltous chloride led to staurosporinone (293) in 40% yield (790) (Scheme 5.248). 

The lithium cation from lithium trifluoromethanesulfonate abstracts fluoride from the substrate. This system has also been used as part of the diethyl cobalt(II)/lithium trifluoromethanesulfonate systems, respectively, which were used for the defluorinations.208... 

The rapid aminolysis of cobalt(llI)-chelated glycine esters in aprotic solvents (Scheme 10 N4 = (en)2 or trien, R = Me, Et, R = H, CHR"C02Et) could be of value in peptide synthesis. The cobalt atom acts as both an N-protecting and an activating group. The synthesis of the chelated amino acid esters has presented some difficulties.207 A recent paper208 describes the use of methyl trifluoromethanesulfonate for the alkylation of chelated amino acids using dry trimethyl phosphate... 

Related Reagents. (5,5)-2,2 -(Dimethylmethylene)bis-(4-/-butyl-2-oxazoline) Bis(dimethylglyoximato)(methyl)(pyridine)-cobalt(III) Copper(II) Trifluoromethanesulfonate (15,95)-1,9-Bis [(/-butyl)dimethylsilyloxy]methyl -5-cyanosemicorrin (5)-2-[2-(Diphenylphosphino)phenyl]-4-phenyloxazoline Ethyl Diazoacetate. 

CoF9N309S3C7H,s, Cobalt(III), [A -(2-ami-noethyl)-1,2-ethanediamine]tris(tri-fluoromethanesulfonato)-, fac-, 22 106 CoF9N409C7H,9, Cobalt(III), bis(l,2-ethane-diamine)bis(trifluoromethanesulfo-nato)-, CU-, trifluoromethanesulfonate, 22 105... 

RuClsHisNs, Ruthenium(III), pentaammine-chloro-, dichloride, 24 255 RuCI]N4C2oH,g 2H2O, Ruthenium(III), bis-(2,2 -bipyridine-lV, IV )dichloro-, cis-, chloride, dihydrate, 24 293 RuCojHOi2C,2, Cobalt, dodecacarbonylhy-dridorutheniumtri-, 25 164 RuFgNsOgS2C27H , Ruthenium(II), (2,2 -bi-pyrichne-N,N )(2,2 6, 2"-terpyridine-N, N, N )(trifluoromethanesulfonato-O)-, trifluoromethanesulfonate,... 

NjQH,], 1,2-Ethanediamine, Ai-(2-aminoethyl)-, cobalt(lll) trifluoromethanesulfonate complexes, 22 106 NjCtH.j, 1,4,7-Triazacyclononanc, cobalt complexes, 23 75 NjNdOuCaHu, Neodymium(III), trini-... 

Cobalt(III) Amine Complexes with Coordinated Trifluoromethanesulfonate 103... 

COBALT(III) AMINE COMPLEXES WITH COORDINATED TRIFLUOROMETHANESULFONATE... 

A. PENTAMMINE(TRIFLUOROMETHANESULFONATO)COBALT(III) TRIFLUOROMETHANESULFONATE, [Co(NH3)sOS02CF3 ](CF3SO)2... 

Complexes of trifluoromethanesulfonate anion with cobalt(III) are labile oward substitution under mild conditions, and they have proved to be useful synthetic precursors to a variety of aminecobalt(III) complexes. The pentaammine-(trifluoromethanesulfonato-O)rhodium(III) ion, which is readily prepared from [Rh(NH3)5Cl]Cl2 in hot CF3SO3H, is also versatile as a synthetic precursor. " Its synthesis and solvolysis to give essentially quantitative yields of the penta-ammineaqua- and hexaamminerhodium(III) ions are described below. The aqua complex has previously been prepared by the base hydrolysis or Ag -induced aquation of [Rh(NH3)5Cl]Cl2 in water, but the present method presents a cleaner and more rapid alternative. The methods for preparation of the [RhCNHj) ] ion have evolved from the procedure of J0rgensen. They involve prolonged reaction of [Rh(NH3)5Cl]Cl2 with ammonia in a pressure vessel at elevated temperature. The solvolysis of [Rh(NH3)5(0S02CF3)](CF3S0j)2 in liquid ammonia is a simple, high-yield, and rapid alternative. 

---