1192-37-6Relevant articles and documents
Kinetics and regioselectivity of ring opening of 1-bicyclo[3.1.0] hexanylmethyl radical
Kantorowski, Eric J.,Le, Daniel D.,Hunt, Caleb J.,Barry-Holson, Keegan Q.,Lee, Jessica P.,Ross, Lauren N.
, p. 1593 - 1596 (2008)
(Chemical Equation Presented) Rate constants for the rearrangement of 1-bicyclo[3.1.0]-hexanylmethyl radical (2) to 3-methylenecyclohexenyl radical (3) and 2-methylenecyclopentyl-1-methyl radical (1) were measured using the PTOC-thiol competition method. The ring-expansion pathway is described by the rate equation, log(k/s-1) = (12.5 ± 0.1) - (4.9 ± 0.1)/θ; the non-expansion pathway is described by log(k/s-1) = (11.9 ± 0.6) - (6.9 ± 0.8)/θ. Employing the slower trapping agent, tri-n-butylstannane, favors methylenecyclohexane over 2-methyl-methylenecyclopentane by more than 120:1 at ambient or lower temperatures.
Platinacyclobutane chemistry: Cis-disubstituted platinacyclobutane complex from bicyclo[4.1.0] heptane
Parsons,Jennings
, p. 1435 - 1437 (1988)
The methodology for the preparation, isolation, and characterization of platinacyclobutanes from cis-disubstituted cyclopropane derivatives is established. In this case the metallacyclobutane was successfully prepared and characterized from bicyclo[4.1.0]
Adjusting the features of active metallocene ziegler systems for their potential use as carbon-carbon coupling catalysts in organic synthesis
Thiele, Sven,Erker, Gerhard
, p. 201 - 207 (1997)
A variety of bent metallocene dichloride/methylalumoxane catalysts, derived from the zirconocene complexes 10, 12-18, have been employed in intramolecular olefin-coupling reactions yielding monomeric or dimeric products. This was achieved by using optimized reaction conditions employing low substrate concentrations (1.0-1.8 M) and rather long reaction times. Under these particular conditions, 1,5-hexadiene was cyclodimerized to give l-methylene-3-(cyclopentylmethyl)cyclopentane (11). 1,6-Heptadiene was cleanly converted to methylenecyclohexane, and cis-1,2-divinylcyclopentane (19) and cis-1,2-divinylcyclohexane (22) were cyclized to yield 2-methylenebicyclo[3.3.0]octane (20) and 7-methylenebicyclo[4.3.0]nonane (23), respectively. In many cases, the cyclization products were accompanied by isomers originating from double-bond shift reactions that often occur rapidly at these catalyst systems under the specific reaction conditions chosen to keep the products in the monomeric regime. VCH Verlagsgesellschaft mbH.
CYCLIZATION OF ALKENYLLITHIUM REAGENTS
Chamberlin, A. Richard,Bloom, Steven H.
, p. 4901 - 4904 (1984)
Alkenyllithium species containing a primary chloride group can be generated efficiently.They undergo subsequent cyclization to alkylidene cycloalkanes of various ring sizes.
Wittig Reagents Bound to Cross-Linked Polystyrenes
Bernard, Margaret,Ford, Warren T.
, p. 326 - 332 (1983)
Insoluble benzyltriarylphosphonium and methyltriarylphosphonium salts have been prepared on 2percent and 8percent divinylbenzene cross-linked polystyrene and on 20percent divinylbenzene cross-linked macroporous polystyrene.Phosphoranes were generated with sodium methoxide or sodium ethoxide in THF and with the dimethylsulfinyl carbanion in Me2SO from the benzyl- and methylphosphonium salts, respectively.Reactions of the phosphoranes with a variety of aldehydes and ketones provided alkenes in 73-96percent yields (by GLC analysis) with the 2percent cross-linked polymer, 52-77percent yields with the 8percent cros s-linked polymer, and 72-87percent yields with the 20percent cross-linked macroporous polymer.The rates of phosphorane generation and alkene formation depend on the polymer, decreasing in the order 2percent > 20percent macroporous > 8percent cross-linked.The fraction of E double bond product from the benzylphosphonium salt and either benzaldehyde or cinnamaldehyde is greater with the 20percent cross-linked macroporous polymer than with the 2percent cross-linked polymer.The byproduct polymer-bound phosphine oxides were reduced to phosphines with trichlorsilane, and the phosphines were reused for Wittig synthesis.A quantitative 31P-NMR analysis of phosphine and phosphine oxide residues in polystyrene gels is reported.
ACTIVATION OF C-H BONDS IN SATURATED HYDROCARBONES. THE SELECTIVE, CATALYTIC FUNCTIONALISATION OF METHYL GROUPS BY MEANS OF A SOLUBLE IRIDIUM POLYHYDRIDE SYSTEM
Felkin, Hugh,Fillebeen-Khan, Tauqir,Holmes-Smith, Rupert,Yingrui, Lin
, p. 1999 - 2000 (1985)
The selective, catalytic conversion of methylcyclohexane into methylenecyclohexane at 100 deg C, and of n-hexane into 1-hexene at 45 deg C, has been effected using bis(triisopropylphosphine)iridium pentahydride and an olefin (neohexene) as a hydrogen acceptor; with this system, approximate relative reactivities of C-H bonds in saturated hydrocarbons are: sec-alkyl-H, 1; iso-alkyl-H, 8; n-alkyl-H, >60.
THE EFFECTIVENESS OF A WEAK BASE IN THE OLEFIN SYNTHESIS FROM β-HYDROXYALKYLPHOSPHONATES
Kawashima, Takayuki,Ishii, Takafumi,Inamoto, Naoki
, p. 1097 - 1100 (1984)
β-Hydroxyalkylphosphonates were treated with a weak base such as potassium carbonate in N,N-dimethylformamide to give the corresponding olefins in good yields.
THE DIMESITYLBORON GROUP IN ORGANIC SYNTHESIS. 4. THE 'BORON WITTIG' REACTION
Pelter, Andrew,Singaram, Bakthan,Wilson, John W.
, p. 635 - 636 (1983)
Anions generated α- to a dimesitylboron group readily condense with aldehydes and ketones.Elimination of Mes2BOLi then leads to alkenes in a boron analogue of the Wittig reaction.
NOVEL HISTONE METHYLTRANSFERASE INHIBITORS
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Page/Page column 30; 37, (2021/04/01)
The present invention relates to novel compounds of formula (I) as defined herein. The compounds are inhibitors of histone methyltransferases of the seven-beta-strand family, in particular of KMT9.
Stereoselective Diboration of Spirocyclobutenes: A Platform for the Synthesis of Spirocycles with Orthogonal Exit Vectors
Nóvoa, Luis,Trulli, Laura,Parra, Alejandro,Tortosa, Mariola
supporting information, p. 11763 - 11768 (2021/04/26)
The diastereo- and enantioselective diboration of spirocyclobutenes provides a platform for the rapid preparation of a wide variety of chiral spirocyclic building blocks. The chemoselective functionalization of the carbon-boron bond in the products, including a stereospecific sp3-sp2 Suzuki–Miyaura cross-coupling reaction, provides a powerful tool to control the directionality and the nature of the exit vectors in the spirocyclic framework.
