1- Methyl-1,5-cyclooctadiene

What are the products of the ROMP of 1-methyl-1,5-cyclooctadiene and cis-, iran -cyclodeca-l,5-diene. Xo which copolymer structures are these equivalent ... 

Abbreviations Aik, alkyl AN, acetonitrile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene Cp, cy-clopentadienyl Cp , pentamethylcyclopentadienyl Cy, cyclohexyl dppm, diphenylphosphinome-thane dpme, Ph2PC2H4PMe2 Et, ethyl fod, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octane-dionate HOMO, highest occupied molecular orbital LUMO, lowest unoccupied molecular orbital Me, methyl MO, molecular orbital nbd, norbornadiene Nuc, nucleophile OTf, triflate Ph, phenyl Pr, propyl py, pyridine THE, tetrahydrofuran TMEDA V,V,M,M-tetramethylethylenediamine. 

Abbreviations acac, acetylacetonate Aik, alkyl AN, acetonitrile bpy, 2,2 -bipyridine Bu, butyl cod, 1,5- or 1,4-cyclooctadiene coe, cyclooctene cot, cyclooctatetraene Cp, cyclopentadienyl Cp, pentamethylcyclopenladienyl Cy, cyclohexyl dme, 1,2-dimethoxyethane dpe, bis(diphenyl-phosphino)ethane dppen, cis-l,2-bis(di[Atenylphosphino)ethylene dppm, bis(diphenylphosphino) methane dppp, l,3-bis(diphenylphosphino)propane eda,ethylenediamine Et,ethyl Hal,halide Hpz, pyrazole HPz, variously substituted pyrazoles Hpz, 3,5-dimethylpyrazole Me, methyl Mes, mesityl nbd, notboma-2,5-diene OBor, (lS)-endo-(-)-bomoxy Ph, phenyl phen, LlO-phenanthroline Pr, f opyl py, pyridine pz, pyrazolate Pz, variously substituted pyrazolates pz, 3,5-dimethylpyrazolate solv, solvent tfb, tetrafluorobenzo(5,6]bicyclo(2.2.2]octa-2,5,7-triene (tetrafluorobenzobanelene) THE, tetrahydrofuran tht, tetrahydrothicphene Tol, tolyl. 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

Steric factors may also be important in situations where alternative modes of reaction are available. Dall Asta (44) examined the ring-opening polymerization of 3-methyl-m-cyclooctene. By infrared analysis of the product formed, he obtained quantitative information about the occurrence of head-to-head and head-to-tail successions. More than 90% of the links in the polymethyloctenamer were of the head-to-tail type, but the sterically more hindered and, therefore, unfavored head-to-head links were also observed (about 5%). Ofstead (39) investigated the ring-opening polymerization of some 1,5-cyclooctadienes substituted at one of the two... 

Muscalure 20, the pheromone of the housefly has been prepared from oleic acid or erucic acid, similarly (Z)-l 1-heneicosene 21, the synergist of muscalure was obtained [189]. The intermediate 22 for the pheromone of the Cabbage looper was prepared using (Z)-methyl-4-octenedioate [166bJ, that was obtained by partial ozonolysis of (Z,Z)-l,5-cyclooctadiene. Similarly disparlure 23, the sex attractant of the gypsy moth, has been synthesized by two successive crossed-couplings with (Z)-4-octene dioate [191],... 

The hydrosilylation of butadiene proceeds with palladium compounds even in the absence of phosphines. Other ligands, such as glyoxime, benzonitrile, and 1,5-cyclooctadiene, can be used as effective ligands for the hydrosilylation of butadiene (65, 67). The reaction of trichlorosilane and dichlorosilane with isoprene proceeded regioselectively and stereo-selectively to give Z-l-trichlorosilyl-2-methyl-2-butene (67) (65, 66, 68). No reaction of trimethylsilane with isoprene took place, and this shows the lower reactivity of trialkylsilane. 

Ketone rac-13 was transformed into the corresponding silylenolether and by Pd(II)-mediated Saegusa oxidation [14] into a, -unsaturated ketone rac-14. By alkylative enone transposition comprising methyl lithium addition and pyridinium chlorochromate (PCC) oxidation [15], rac-14 was finally converted into the racemic photo cycloaddition precursor rac-6. In conclusion, the bicyclic irradiation precursor rac-6 was synthesized in a straightforward manner from simple 1,5-cyclooctadiene (11) in nine steps and with an overall yield of 21%. 

Kahn and Chen (87TL1623) performed the regio- and stereospecific reaction of 1,3-cyclooctadiene and acyliminium derivative 79, which resulted exclusively in compounds 80 in 37% yield after chromatographic purification. 79 was prepared by treatment of the A-methylimine of benzal-dehyde with methyl chloroformate in the presence of titanium(IV) chloride. 

Regioselective electrophilic bromination of the carbazole 1025 afforded the 6-bromocarbazole 1026. Cleavage of the methyl ether to 1027 and subsequent nickel-mediated coupling using a dimeric 7i-prenylnickel bromide complex prepared in situ from prenyl bromide 925 and bis(l,5-cyclooctadiene)nickel(0) led directly to siamenol (89) (546) (Scheme 5.151). 

Nan ya et al. (93,94) also reported the reaction of sydnones with Al-methyl- and N-phenylmaleimides. Gribble and Hirth (206) extended the work of Weintraub (207) on the tandem dipolar cycloaddition of sydnones with 1,5-cyclooctadiene to afford diazatetracycloundecanes 305. 

SYNTHESIS OF (45, 55)-[(f -l,5-CYCLOOCTADIENE)- 2-(2-PHEN YL-5-METHYL, 5-DIHYDRO-OXAZOL-4-YL)-1,3-DIPHENYL-2-DIPHENYLPHOSPHINITE-PROPANE IRIDIUM(I)]-TETRAKIS[3,5-BIS(TRIFLUOROMETHYL)PHENYL]BORATE... 

Cyclooctadiene)- 2-(2-phenyl-5-methyl-4,5-dihydro-oxazol-4-yl)-l,3-diphenyl-2-diphenylphosphimte-propane mdium(l)]-tetrakis[3,5-bis(tri-fluoromethyl)phenyl]borate (1.72mg, l.Opmol). The catalyst is available from Strem Chemicals, Inc. (catalogue no. 77-5020). 

J. (n4-l, 5-CYCLOOCTADIENE)TETRAKIS(METHYL-HYDRAZINE)RUTHENIUM(II) BIS[HEXAFLUORO-PHOSPHATE(l -)]... 

Bis(l,5-cyclooctadiene)nickel, Ni(cod)2, is prepared according to the literature,4 as is tricyclohexylphosphine, tcyp.5 The latter must be recrystallized from rigorously dried diethyl ether. Methacrylamide (2-methyl-2-pro-penamide) was purchased from Tokyo Kasei (99% purity, authors) or from Ega Chemie (98-99% purity, checkers). Allylcyanide (3-butenenitrile) was purchased from Tokoyo Kasei (99% purity, authors) or from Merck-Schuchardt (98% purity, checkers). 

A tetrahydrofuran (THF) (20 mL) solution of a mixture of 1.7 g (6.2 mmol) of bis(l,5-cyclooctadiene)nickel, Ni(cod)2, 1.7 g (6.2 mmol) of tricyclohexylphosphine, and 1.1 g (13 mmol) of 2-methyl-2-propenamide (methacrylamide) is stirred for 6 h at room temperature in a nitrogen-filled 50-mL Schlenk tube equipped with a magnetic stirring bar. A greenish-yellow precipitate results. The reaction mixture is cooled to — 30 °C, and after 2 h the solvent containing... 

C2H,N, Pyridine, 3,5-dimethyl-palladium complex, 26 210 CbHsNO, Benzoyl isocyanide chromium com-C HbO, Ethanone, 1-phenyl-manganese complex, 26 156-158 CBH, 02, Methyl benzoate chromium complex, 26 32 C H i, o-Xylylene magnesium complex, 26 147 ChH P, Phosphine, dimethylphenyl-iron complex, 26 61 ruthenium complex, 26 273 ChH12, 1,5-Cyclooctadiene iridium complex, 26 122 ruthenium complexes, 26 69-72, 253-256 ChH OjPS, 2-Butenedioic acid, 2-(dimethylphosphinothioyl)-dimethyl ester, manganese complex, 26 163... 

N4F,2P2RuCl6H24, Ruthenium(II), tetrakis-(acetonitrile)(r)J-, 1,5-cyclooctadiene)-bis[hexafluorophosphate( 1 —)], 26 72 NjFeOGoHjft, Iron, carbonyltetrakis(2-iso-cyano-1,3-dimethylbenzene)-, 26 57 N4Li2Si2C2ftH5ft, Lithium, p.-[(a,cx, l,2-T) a,a, 1, 2-ti- 1,2-phenylenebis[(trimethyl-silyl)methylene]]bis(Af, V,lV, Ar-tetra-methyl-l,2-ethanediamine)di-,... 

N,B2RuCftnH7ft, Ruthenium(II), (nJ-l,5-cyclooctadiene)tetrakis(methyl-hydrozine)-... 

RuCoO,SC Ruthenium, nonacarbonyl-p.,-thio-dicobalt-, 26 352 RuCo2OuCi, Ruthenium, undecacar-bonyldicobalt-, 26 354 RuCojNOi2C 2H2(i, Ruthenate(l -), dodeca-carbonyltricobalt-tetraethylammonium, 26 358 RuF12N4P2C (,H24, Ruthenium(II), tetrakis-(acetonitrile) (n4-1,5-cyclooctadiene)-bis[hexafluorophosphate(l -)], 26 72 RuF 2NBP2Ci2H36, Ruthenium(II), (V cyclooctadiene)tetrakis(methyl-hydrazine)-... 

U.yUNSATURATED KETONES Bis-(l,5-cyclooctadiene)nickel(0). Dimethyl-(phenylthio)aluminum. a-Phenylglycine methyl ester. Phcnylselcnoacetaldchydc. Zinc-Silver couple. 

An iron catalyst formed from a C2-symmetric l,4-diaza-l,3-diene-FeCl2 complex and an organomagnesium compound promotes the cyclo-codimerization of isoprene and trans-1,3-pentadiene to give 1,7-di-methyl-1,5-cyclooctadiene in a fair ee (Scheme 110) (270). 

N-Benzyl-N-methoxymethyl-N-(tri-methylsilyl)methylamine, 31 Bis( 1,5-cyclooctadiene)nickel(0), 35 Lithium diisopropylamide, 163 N-Methyl-N, O-bis(trimethylsilyl) -hydroxylamine, 187 Titanium(IV) chloride-N-Methylani-line, 310... 

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