16736-42-8Relevant articles and documents
Preparation and Reactions of Cyclic and Acyclic Allene Complexes of Zirconocene
Yin, Jianguo,Jones, W. M.
, p. 4395 - 4406 (1995)
The zircone ?-complex of 3-methyl-1,2-butadiene (1,1-dimethylallene) cannot be prepared by simple ligand substitution due to rapid coupling of the initially formed complex with the unreacted allene.This problem was circumvented by generating the allene complex by β-hydrogen elimination from a pre-formed sigma complex.This appears to be a potentially general way to prepare allene complexes of zirconocene if the allene precursor has no cis-vinyl hydrogen.This method has been successfully used to prepare zirconocene complexes of 3-methyl-1,2-cycloheptadiene, 3-methyl-1,2-cyclohexadiene and 4-phenyl-1,2,3-cyclohexatriene.Attempts to prepare a complex of 3-methyl-1,2-cyclopentadiene failed.Selected reactions of two of these cumulene complexes and their coupling products are reported.
An Efficient Electrochemical Coupling of Allylic Halides by Using a Copper Anode
Tokuda, Masao,Endate, Kazuhiro,Suginome, Hiroshi
, p. 945 - 948 (1988)
A new electrolytic method for an efficient coupling of allylic halides by the use of a copper anode and a platinum cathode in the precence of sodium iodide is described.A method which avoids a loss of the copper anode owing to dissolution is also described.
THERMISCHE STABILITAET VON BIS(ALK-2-ENYL)ZINK-VERBINDUNGEN
Lehmkuhl, Herbert,Doering, Ingo,Nehl, Hans
, p. 7 - 12 (1981)
The dialk-2-enylzinc compounds I-III react slowly at 20 to 50 deg C by addition of the Zn-C bond to the C=C bond of an alk-2-enyl group to give oligomers from which the alkenes XIII-XV are released on hydrolysis.For I-III homolytic cleavage of the Zn-Callyl bond, followed by coupling of the allyl radicals to give the alkadienes V-VII, IX and XI predominates above 50 deg C.IV decomposes mainly homolytically even at 20 deg C.
Coupling reaction of terminal allenes with themselves or acetylenes mediated by (η2-propene)Ti(O-i-Pr)2: some new selectivities and synthetic application
Hideura, Daigaku,Urabe, Hirokazu,Sato, Fumie
, p. 271 - 272 (1998)
Treatment of an allene alone or with an acetylene with (η2-propene)Ti(O-i-Pr)2 generates a new titanacycle, which reacts with some electrophiles to give useful intermediates for organic synthesis.
En route to stable all-carbon-substituted silylenes: Synthesis and reactivity of a bis(α-spirocyclopropyl)silylene
Redies, Kai M.,Fallon, Thomas,Oestreich, Martin
supporting information, p. 3235 - 3238 (2014/08/05)
The synthesis of a bis(α-spirocyclopropyl)silylene is reported and its reactivity revealed. Liberation of the silylene was accomplished by UV-light-mediated photolysis of a trisilane precursor. Insertion and addition reactions prove the existence and versatility of this new family of bis(α-spirocyclopropyl)-substituted silylenes. Substitution on the flanking cyclopropyls for improved steric shielding of the reactive center remains challenging.
Catalyst-free suzuki-type coupling of allylic bromides with arylboronic acids
Scrivanti, Alberto,Beghetto, Valentina,Bertoldini, Matteo,Matteoli, Ugo
supporting information; experimental part, p. 264 - 268 (2012/02/04)
The coupling of arylboronic acids with electron-rich allylic bromides is accomplished in the absence of any transition-metal catalyst through conventional heating. The reaction is completely regioselective, affording only the α-coupled product, and can be carried out under mild aerobic conditions in an organic solvent; the presence of a base is required. Copyright
The substrate specificity of β,β-carotene 15,15′-monooxygenase
Wirtz, Gabriele M.,Bornemann, Claus,Giger, Alfred,Mueller, Robert K.,Schneider, Heinz,Schlotterbeck, Goetz,Schiefer, Gerhard,Woggon, Wolf-Dietrich
, p. 2301 - 2315 (2007/10/03)
The synthesis of several substrate analogues of the enzyme β,β-carotene 15,15′-monooxygenase is reported. The substrate specificity of enriched enzyme fractions isolated from chicken intestinal mucosa was investigated. Regarding substrate binding/cleavage, these experiments demonstrate that i) any deviation from the rod-like β,β-carotene structure is not tolerated, ii) one 'natural', unsubstituted β-ionone ring is required, iii) the position and presence of the Me groups attached to the polyene chain is significant. These results suggest a hydrophobic barrel-like substrate binding site in which the protein's amino acid residues through interaction with the Me groups, direct the central C=C bond in binding distance to the active site's metal-oxo center, supporting the unique regiospecificity of cleavage to retinal (provitamin A).
New Electrochemical Synthesis of Ketones from Organic Halides and Carbon Monoxide
Ocafrain, Maitena,Devaud, Marguerite,Troupel, Michel,Perichon, Jacques
, p. 2331 - 2332 (2007/10/02)
The dissolution of a stainless steel anode provides catalytic nickel species which enable the efficient synthesis of ketones by electrolysis of organic halides in DMF in the presence of bipyridine and carbon monoxide.
- the Wet Chemical Route to a Highly Reactive Titanium Hydride
Becker, Beate,Bogdanovic, Borislav
, p. 476 - 482 (2007/10/02)
The reaction between catalytically prepared magnesium hydride (MgH2*) and in a molar ratio of 1.5:1 in THF yields a highly pyrophoric, X-ray amorphous titanium hydride precipitate with the composition (2).This novel titanium hydride precipitate with the composition (2).This novel titanium hydride has been characterized through hydrolysis and iodolysis, as well as through thermolysis to Ti* and H2 in the solid state and in organic solvents. 2 is slightly soluble in THF and proves itself as an active reagent in a variety of reactions. - Keywords: Magnesium Hydride, Titanium Hydride, McMurry-Reaction, Titanium
Stereoselective Addition Reactions of Chiral N-Benzylidene-p-toluenesulfinamides. Asymmetric Syntheses of β- and γ-Amino Acids
Hua, Duy H.,Miao, Shou Wu,Chen, Jin Shan,Iguchi, Sadahiko
, p. 4 - 6 (2007/10/02)
Chiral N-benzylidene-p-toluenesulfinamides 2 were prepared by the reaction of benzonitril with alkyllithium in ether followed by (-)-l-menthyl (S)-p-tolylsulfinate.Treatment of 2 with allylmagnesium bromide in ether at 0 deg C gave the adducts (R)-7 with excellent stereoselectivity.Pure chiral sulfinamides 7 were converted into β- and γ-amino acids in four and five steps, respectively.