Chlorobis palladium

The reaction of racemic Sb-chiral l-phenyl-2-trimethylsilylstibindole with the optically active ortho-palladated benzylamine derivative, di-p-chlorobis (S)-2-[l-dimethylamino)ethyl]phenyl-C,N dipalladium, leads to diastereomeric complexes which were used for the separation of the enantiomers of the stibindoles.65 The molecular structures of the diastereomeric palladium complexes are depicted in Fig. 4. 

Herrmann WA, Brossmer C, Reisinger CP, Riermaier T, Ofele K, Beller M (1997) Coordination chemistry and mechanisms of metal-catalyzed C-C coupling reactions. Part 10. Palladacycles efficient new catalysts for the Heck vinylation of aryl halides. Chem Eur J 3 1357-1364 Iyer S, Jayanthi A (2001) Acetylferrocenyloxime palladacycle-catalyzed Heck reactions. Tetrahedron Lett 42 7877-7878 Iyer S, Ramesh C (2000) Aryl-Pd covalently bonded palladacycles, novel amino and oxime catalysts di- x-chlorobis(benzaldehydeoxime-6-C,AT)dipalla-dium(II), di- x-chlorobis(dimethylbenzylamine-6-C,A)dipalladium(II) for the Heck reaction. Tetrahedron Lett 41 8981-8984 Jeffery T (1984) Palladium-catalysed vinylation of organic halides under solid-liquid phase transfer conditions. J Chem Soc Chem Commun 1287-1289 (b) idem,... 

Dimethylthexylsilyl trifluoromethane-sulfonate, 74 Diphenylsilane, 153 Diphenylsilane-Di- x-chlorobis(l,5-cyclooctadiene)dirhodium, 153 Diphenylsilane-Palladium(II) chloride-Triphenylphosphine, 126 Diphenylsilane-Tetrakis(triphenyl-phosphine)palladium(0)-Zinc chloride, 126... 

Resin 4 (R1 = CH3) (50 mg, 0.014 mmol) was weighed into a conical Personal Chemistry Smith process vial equipped with a conical-shaped stir bar. To the resin was added 4-fluorophenylboronic acid (11 mg, 0.08 mmol), DMF (1 ml), 2 M aqueous sodium carbonate (80 pi), and di-chlorobis(triphenylphosphine)palladium(II) (1-2 mg). The heavy walled glass vial was crimp sealed and placed on the Gilson platform. The micro-wave program was set to a 5 min duration at 180° on the normal absorption setting and the vial was then processed. After completion, the vial was decrimped and resin 5 (R1 — CH3, R2 = 4-F-phenyl) was transferred to a fritted tube and washed with DMF, H20, MeOH, and DCM (3x each). 

Phosphoryl diazomethanes react with 2,6-di-/erf-butylthiopyrylium ion (26) in the presence of triethylamine to give the corresponding 4-(di-azomethyl)-4//-thiopyrans 349-353. Reaction of compound 349 or 350 with di-/x-chlorobis-(7r-allyl)palladium(Il), instead of the expected thiepine derivative, afforded the anhydrobase 354 or 355, respectively (85T811). 

Resolution of the racemic 7-/i-tolyldinaphtho[2,l-4 T,2 -optically active palladium complexes (with O.Sequiv of dimeric optically active di-p.-chlorobis (4)-2-[T(dimethylamino)-ethyl]phenyl-(7,M dipalladium(n)) 29 is a rare example of a reaction giving a product with CN 4 (Equation 6). The diastereomeric mixture thus produced could not be separated by fractional recrystallization from a variety of solvents or by column chromatography, because the optically active 7-A-tolyldinaphtho[2,l-4 l, 2 -palladium complex 48. Also the complex prepared from enantiomerically pure R-(-)-stibole 16 racemizes due to fluxionality (NMR estimated at elevated temperatures) <2001TL441, 2003YZ577>. 

Cyclopentenes Benzy chlorobis(triphenyl-phosphine)palladium( lI). Cyclopropenone 1,3-propanediyl ketall. Di-p,-carbonylhexa-carbonyldicobalt. 

T reatment of di-/i-chlorobis[a-4-6- -(3-oxocholestenyl)palladium(II)] (224) with DBU yielded dienone 225 in 11% yield in dichloromethane and in 35% yield in tetrahydrofuran (80AJC1537). 

Conversion of norbornadiene to nortricyclenes can also be achieved with organomercurials. This reaction proceeds via transmetalation to form a c-bonded organopalladium system which inserts norbornadiene. Thus an enrfo-cw-addition is observed. Conversions of this type were observed in the phenylation of dichloro(t -norbornadiene)palladium either with diphenyl-mercury or, more conveniently, with sodium tetraphenylborate to give di-/r-chlorobis(2 5,6-t -c ffo-3-phenylbicyclo[2.2.1]hept-e /o-2-yl)palladium (30) via cis addition.By contrast, the analogous platinum complex did not give a phenylation product. The palladium complex 30 underwent reversible ring closure to a nortricyclenyl complex 31 with pyridine. ... 

Similar dicarborating cis-exo additions are achieved with up to 99 % yield if aryl or vinyl halides and various organotin compounds, such as vinyl-, phenyl-, ethynyl- and allyl(tributyl)tin systems, are added to norbornene in the presence of tetrakis(triphenylphosphane)palladium(0) or di-chlorobis(triphenylphosphane) as catalyst precursor7,30,80-81. Also reported are cis-exo dicarbo-rative additions to the norbornene skeleton, and their application to the synthesis of prostaglandin endoperoxide analogs, which employ stoichiometric amounts of palladium compounds16. 

An interesting class of cationic polyyne polymers 187 was prepared by reaction of the bimetallic complex, p-butadiynediyl-bis[/ra//i--chlorobis(tri-//-butylphosphine)palladium], with an equimolar amount of 4,4 -bipyridyl in... 

DIENES Bis-3-methyl-2-butyl-borane. Chlorobis(cyclopentadienyl)-hydridozirconium. Formylmethylene-triphenylphosphorane. LithioaUyl-trimethylsilane. Methylcopper. Pal-ladium(II) acetate. Palladium(ll) chloride. Tetrakis(triphenylphosphine)-palladium(O). 

KETONES 1,3-Benzodithiolylium perchlorate. Benzyl(chloro)bis(triphenyl-phosphine)palladium. Chlorobis-(cyclopentadienyl)hydridozirconium. Iron carbonyl. Manganese(ll) iodide. Silver acetate. Thionyl chloride. Tosylmethyl isocyanide. Tri-p-carbonylhexacarbonyldiiron. 

Di-chloro-bi [S-chloro-2-[(4-chlorophenyl)(hydroxyimino)methyl]phenyl-C]-di-palladium Ndjera Catalyst I, di-p-chlorobis[5-chloro-2-[(4-chlorophenyl)(hydroxyimino-KN)methyl]phenyl-KC]-palladium (H) dimer [287410-78-0] has M 814.0 and m 208-210°. [Alonso, Najera and Pacheco Org Lett 1 1823 2000]. 

C2 3H1sCoNgOuPd, (TetracarbonyIcobalto)pyridine(N-(phenylimino)-a-methylben2ylidenimino-2-C,N)palladium(lI), 43B, 991 C2 3H2 2ClPZr, Chlorobis(7 -cyclopentadienyl)(diphenylphosphinomethyl )zirconium(lV), 46B, 805... 

C22ClN03P2Pd, trans-(1-p-Tolyl-3-oxo-2-(E)-carbomethoxymethyl-idene-2,3-dihydropyrrole)chlorobis(triethylphosphine)palladium(II), 44B, 713... 

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