5968-21-8Relevant academic research and scientific papers
Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins
Lan, Yu,Liu, Qiang,Liu, Shihan,Liu, Xufang,Rong, Xianle
supporting information, p. 20633 - 20639 (2021/12/17)
Chiral cyclic olefins, 1-methylcyclohexenes, are versatile building blocks for the synthesis of pharmaceuticals and natural products. Despite the prevalence of these structural motifs, the development of efficient synthetic methods remains an unmet challenge. Herein we report a novel desymmetric isomerization of exocyclic olefins using a series of newly designed chiral cobalt catalysts, which enables a straightforward construction of chiral 1-methylcyclohexenes with diversified functionalities. The synthetic utility of this methodology is highlighted by a concise and enantioselective synthesis of a natural product, β-bisabolene. The versatility of the reaction products is further demonstrated by multifarious derivatizations.
Determination des pKa et reaction d'ouverture acide de quelques alkyl-2 et aryl-2 aziridines
Lamaty, Gerard,Sanchez, Jean-Yves,Sivade, Andre,Wylde, James
, p. 1261 - 1266 (2007/10/02)
Some 2-para substituted aryl aziridines (with pY = CH3O-, CH3-, H-, and Cl-) have been prepared.Their ring opening reaction in acidic medium has been studied and compared with those of two aliphatic aziridines : 2 methyl- and 2,2 dimethyl-aziridine.In aqueous solvent, the addition of HCl, HBr, and HI to the aromatic aziridines leads exclusively to the secondary halogen product, due to the nucleophilic attack on the benzylic carbon.The hydrolysis reaction competes with the addition reaction and is very important for the para methoxy 2-phenyl aziridine.In ethyl alcohol (anhydrous solvent), the hydrohalogenation reaction leads exclusively to halogeno amine with a secondary halogen.The solvolysis reaction, leading to amino-ether, is far less important than in water (excepted for the para methoxy 2-phenyl aziridine).In both solvents, the importance of the solvolysis depends on the HX concentration, as well as the nucleophilic strength of the halogen.The pKa values of these aziridines have been measured, as well as those of 2-phenyl 1-amino 2-ethanol.A linear plot is obtained for the pKa versus ?+p of Brown ; the slopes are respectively -2.8 and 0.Therefore the aromatic aziridines seem to have a behavior similar to that of anilines.
Absorption, Circular Dichroism, and Nuclear Magnetic Resonance Studies of Bis(acetylacetonato)cobalt(III) Complexes Containing 2-Aminoalkylphosphine Chelates with Phosphorus and Nitrogen Donor Atoms
Kashiwabara, Kazuo,Kinoshita, Isamu,Ito, Tasuku,Fujita, Junnosuke
, p. 725 - 732 (2007/10/02)
Bis(acetylacetonato)cobalt(III) complexes containing a variety of 2-aminoalkylphosphines, NH2CH2CH2P(C6H5)2, (CH3)2NCH2CH2P(C6H5)2, (S)-NH2CH(CH3)CH2P(C6H5)2, rac-NH2CH2CH2P(CH3)(C6H5), (R)-NH2CH2CH2P(C4H9)(C6H5) and NH2CH2CH2P(CH3)2, and a diphosphine, (C6H5)2PCH2CH2P(C6H5)2 were prepared and resolved (or separated) into optical isomers by SP-Sephadex column chromatography.Absorption, circular dichroism, and 1H and 13C NMR spectra of the new complexes were measured and the results compared with those of the related complexes.Positions of the 2-aminoalkylphosphine and the related ligands in the spectrochemical series were as follows; CN- > NH2CH2CH2P(CH3)2 > (C6H5)2PCH2CH2P(C6H5)2 > NH2CH2CH2P(CH3)(C6H5) NH2CH2CH2P(C4H9)(C6H5) > NH2CH(CH3)CH2P(C6H5)2 NH2CH2CH2P(C6H5)2 NH2CH2CH2NH2 > (CH3)2NCH2CH2P(C6H5)2.For the 13C NMR spectra, all the signals including those due to two diastereotopic phenyl groups on a phosphorus atom were assigned, and the chemical shifts and the coupling constants were determined.The methyl and carbonyl carbons which are trans to a phosphorus atom give a doublet signal due to four-bond (4J(C,P) = 6-7 Hz) and three-bond 3J(C,P) = 2-3 Hz) couplings, respectively, through a cobalt(III) ion.
