PHOTOCHEMICAL-REACTIONS OF TRANSITION METAL-OLEFIN COMPLEXES .11. [4+6]-CYCLOADDITION OF TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE IN TRICARBONYL-ETA-6-1,3,5-CYCLOHEPTATRIENE-CHROMIUM(0)

1985-01-01
The photochemical reaction of tricarbonyl-η6-1,3,5-cycloheptatriene-chromium(0) (I) with tricyclo[6.3.0.02,7]undeca-3,5-diene (II) in n-pentane at 248 K yields the [4 + 6]-cycloadduct tricarbonyl-η6-pentacyclo[7.6.2.110,15.02,8.03,7]octadeca-11,13,16-triene-chromium(0) (III). Detachment of the pentacyclic triene ligand from chromium can be achieved with trimethylphosphite. The constitutions of complex III and of the pentacyclic hydrocarbon IV were determined by spectroscopic means.
JOURNAL OF ORGANOMETALLIC CHEMISTRY

Suggestions

Aminophosphine-palladium(II) complexes: Synthsesis, structure and applications in Suzuki and Heck cross-coupling reactions
AYDEMİR, MURAT; BAYSAL, AKIN; ŞAHİN, Ertan; Gumgum, Bahattin; Özkar, Saim (Elsevier BV, 2011-11-30)
Reaction of furfurylamine with 1 or 2 equivalents of PPh2Cl in the presence of Et3N, proceeds under anaerobic conditions in thf to give furfuryl-2-(N-diphenylphosphino)amine, Ph2PNHCH2-C4H3O, 1 and furfuryl-2-(N,N-bis(diphenylphosphino)amine), (Ph2P)(2)NCH2-C4H3O, 2, respectively. The reactions of 1 and 2 with MCl2(cod) (M = Pd, Pt; cod = 1,5-cyclooctadiene) or Pt(CH3)(2)(cod) yield complexes [M(Ph2PNHCH2-C4H3O)(2)Cl-2] (M= Pd 1a, Pt 1b), [Pt(Ph2PNHCH2-C4H3O)(2)(CH3)(2)] (1c), and [M((Ph2P)(2) NCH2-C4H3O)Cl...
Ruthenium complexes of aminophosphine ligands and their use as pre-catalysts in the transfer hydrogenation of aromatic ketones: X-ray crystal structure of thiophene-2-(N-diphenylthiophosphino)methylamine
AYDEMİR, MURAT; BAYSAL, AKIN; Özkar, Saim; Yildirim, Leyla Tatar (Elsevier BV, 2011-03-24)
Reaction of thiophene-2-methylamine with one or two equivalents of PPh2Cl in the presence of NEt3, proceeds in thf to give thiophene-2-(N-diphenylphosphino)methylamine, la and thiophene-2-(N, N-bis(diphenylphosphino))methylamine, 2a respectively, under anaerobic conditions. Oxidations of la and 2a with aqueous hydrogen peroxide, elemental sulfur or gray selenium in thf gives the corresponding oxides, sulfides and selenides [Ph2P(E)NHCH2-C4H3S] (E: O 1b, S 1c, Se 1d) and [(Ph2P(E))(2)NCH2-C4H3S], (E: O 2b, S...
A new and efficient chemoenzymatic route to both enantiomers of alpha '-acetoxy and alpha '-hydroxy-alpha-methoxy cyclic enones
Demir, Ayhan Sıtkı; Caliskan, Z; Aydin, AE; Bicer, I (Elsevier BV, 2006-03-06)
A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting alpha'-acetoxy and alpha'-hydroxy-alpha-methoxy cyclic enones starting from alpha-hydroxy cyclic enones is described. Protection of 1,2-diketones, manganese(III) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of alpha'-acetoxy enones gives acetoxy enones 3a-d and hydroxy enones 4a-d with high enantiomeric excesses (up to 99%) and good yields. The transesterification of rac-4b in the presence of DMAP af...
Carbonyltungsten(0) complexes of acryloylferrocene: Synthesis and characterization
Boga, Dilek Ayse; Özkar, Saim (Elsevier BV, 2006-07-15)
Photolysis of hexacarbonyltungsten(0) in the presence of acryloylferrocene in n-hexane solution at 10 C yields pentacarbonyl(eta(2)-acryloylferrocene)tungsten(0) (1) as the only photo-substitution product, different from the general reaction pattern observed for the Group 6 metal carbonyls with other olefins. W(CO)5(eta(2)-acryloylferrocene) (1) decomposes in solution to the parent hexacarbonyltungsten(0) and free acryloylferrocene. Trimethylphosphite was introduced as ligand into the molecule to increase t...
Asymmetric synthesis of novel 1,4-aminoalcohol ligands with norbornene and norbornane backbone: use in the asymmetric diethylzinc addition to benzaldehyde
Tanyeli, Cihangir; ERDEM, Mine; ÇAKIR, Esen; KESKİN, Eda (Elsevier BV, 2007-09-27)
The asymmetric synthesis of cis-1,4-aminoalcohols with norbornene and norbornane backbone was performed starting with (2S, 3R)-(-)-cis-hemiester 1 (98% ee). Chemoselective amination with HMPTA followed by Grignard reactions and subsequent LAH reductions afforded compounds 5a-d. cis-Hemiester 1 was also transformed into chiral ligands 7a-f and 9a-d with the DCC coupling method followed by LAH reduction using acyclic, heterocyclic amines and various aniline derivatives and p-toluenesulfonamide, respectively. ...
Citation Formats
S. Özkar, “PHOTOCHEMICAL-REACTIONS OF TRANSITION METAL-OLEFIN COMPLEXES .11. [4+6]-CYCLOADDITION OF TRICYCLO[6.3.0.0(2.7)]UNDECA-3,5-DIENE IN TRICARBONYL-ETA-6-1,3,5-CYCLOHEPTATRIENE-CHROMIUM(0),” JOURNAL OF ORGANOMETALLIC CHEMISTRY, pp. 229–233, 1985, Accessed: 00, 2021. [Online]. Available: https://hdl.handle.net/11511/69981.