928-92-7Relevant articles and documents
Ionic Iodocarbocyclization Reactions of 4-Alkenyl- and 4-Alkynylmalonate Derivatives
Kitagawa, Osamu,Inoue, Tadashi,Hirano, Keiko,Taguchi, Takeo
, p. 3106 - 3112 (1993)
The cyclization reactions of dimethyl 4-alkenylmalonate derivatives 1a-d in the presence of I2 and Ti(Ot-Bu)4 proceed in a highly regio- and stereocontrolled manner (5-exo cyclization and trans addition) to give (iodoalkyl)cyclopentane derivatives 2 or bicyclic lactones 3 through the displacement of the iodide of 2 by an ester group.Iodocarbocyclization reactions of dimethyl malonates 1g-i or dimethyl malonates 1j and 1k proceed regio- and stereoselectively to give fused ring compounds or spiro compounds, respectively, as single isomers.Similar reactions of 4-alkynyl derivatives 5 give preferentially E-iodomethylene cyclopentane derivatives 6.An ionic mechanism rather than a radical mechanism is suggested on the basis of the regioselectivity and stereospecificity of the above reactions.
Cobalt-Catalyzed Intermolecular Hydrofunctionalization of Alkenes: Evidence for a Bimetallic Pathway
Zhou, Xiao-Le,Yang, Fan,Sun, Han-Li,Yin, Yun-Nian,Ye, Wei-Ting,Zhu, Rong
supporting information, p. 7250 - 7255 (2019/05/16)
A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use of hypervalent iodine(III) reagents that enables a mechanistic shift from conventional cobalt-hydride catalysis. Key evidence was found supporting a unique bimetallic-mediated rate-limiting step involving two distinct cobalt(III) species, from which a new carbon-heteroatom bond is formed.
Dynamic ?-Bonding of Imidazolyl Substituent in a Formally 16-Electron Cp Ru(2-P, N)+ Catalyst Allows Dramatic Rate Increases in (E)-Selective Monoisomerization of Alkenes
Paulson, Erik R.,Moore, Curtis E.,Rheingold, Arnold L.,Pullman, David P.,Sindewald, Ryan W.,Cooksy, Andrew L.,Grotjahn, Douglas B.
, p. 7217 - 7231 (2019/08/27)
Alkene isomerization can be an atom-economical approach to generating a wide range of alkene intermediates for synthesis, but fully equilibrated mixtures of disubstituted internal alkenes typically contain significant amounts of the positional as well as geometric (E and Z) isomers. Most classical catalyst systems for alkene isomerization struggle to kinetically control either positional or E/Z isomerism. We report coordinatively unsaturated, formally 16-electron Cp Ru catalyst 5, which facilitates simultaneous regio- A nd stereoselective isomerization of linear 1-alkenes to their internal analogues, providing consistent yields of (E)-2-alkenes greater than 95%. Because nitrile-free catalyst 5 is more than 400 times faster than previously published nitrile-containing analogues 2 + 2a, very reasonable 0.1-0.5 mol % loadings of 5 complete ambient-temperature reactions within 15 min to 4 h. UV-vis, NMR, and computational studies depict the imidazolyl fragment on the phosphine as a hemilabile, four-electron donor in 2-P,N coordination. For the first time, we show direct experimental evidence that the PN ligand has accepted a proton from the substrate by characterizing the intermediate Cp Ru[??3-allyl][1-P)P-N+H], which highlights the essential role of the bifunctional ligand in promoting rapid and selective alkene isomerizations. Moreover, kinetic studies and computations reveal the role of alkene binding in selectivity of unsaturated catalyst 5.
Rhenium-catalyzed deoxydehydration of renewable triols derived from sugars
Wozniak, Bartosz,Li, Yuehui,Tin, Sergey,De Vries, Johannes G.
supporting information, p. 4433 - 4437 (2018/10/17)
An efficient method for the catalytic deoxydehydration of renewable triols, including those obtained from 5-HMF, is described. The corresponding unsaturated alcohols were obtained in good yields using simple rhenium(vii)oxide under neat conditions and ambient atmosphere at 165 °C.
Pd(II)-Catalyzed [4 + 2] Heterocyclization Sequence for Polyheterocycle Generation
Glaisyer, Elizabeth L.,Watt, Michael S.,Booker-Milburn, Kevin I.
supporting information, p. 5877 - 5880 (2018/09/25)
A new Pd(II)-catalyzed cascade sequence for the formation of polyheterocycles, from simple starting materials, is reported. The sequence is applicable to both indole and pyrrole substrates, and a range of substituents are tolerated. The reaction is thought to proceed by a Pd(II)-catalyzed C-H activated Heck reaction followed by a second Pd(II)-catalyzed aza-Wacker reaction with two Cu(II)-mediated Pd(0) turnovers per sequence. The sequence can be considered a formal [4 + 2] heterocyclization.
Total Synthesis and Biological Evaluation of Siladenoserinol A and its Analogues
Yoshida, Masahito,Saito, Koya,Kato, Hikaru,Tsukamoto, Sachiko,Doi, Takayuki
supporting information, p. 5147 - 5150 (2018/03/26)
The total synthesis of siladenoserinol A, an inhibitor of the p53–Hdm2 interaction, has been achieved. AuCl3-catalyzed hydroalkoxylation of an alkynoate derivative smoothly and regioselectively proceeded to afford a bicycloketal in excellent yield. A glycerophosphocholine moiety was successfully introduced through the Horner–Wadsworth–Emmons reaction using an originally developed phosphonoacetate derivative. Finally, removal of the acid-labile protecting groups, followed by regioselective sulfamate formation of the serinol moiety afforded the desired siladenoserinol A, and benzoyl and desulfamated analogues were also successfully synthesized. Biological evaluation showed that the sulfamate is essential for biological activity, and modification of the acyl group on the bicycloketal can improve the inhibitory activity against the p53–Hdm2 interaction.
Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran
Bui, Phuong P.,Oyama, S. Ted,Takagaki, Atsushi,Carrow, Brad P.,Nozaki, Kyoko
, p. 4549 - 4558 (2016/07/12)
The reactions of 2-methyltetrahydropyran (2-MTHP, C6H12O) on Ni2P/SiO2 provide insights on the interactions between a cyclic ether, an abundant component of biomass feedstock, with a transition-metal phosphide, an effective hydrotreating catalyst. At atmospheric pressure and a low contact time, conditions similar to those of a fast pyrolysis process, 70% of products formed from the reaction of 2-MTHP on Ni2P/SiO2 were deoxygenated products, 2-hexene and 2-pentenes, indicating a good oxygen removal capacity. Deprotonation, hydrogenolysis, dehydration, and decarbonylation were the main reaction routes. The reaction sequence started with the adsorption of 2-MTHP, followed by ring-opening steps on either the methyl substituted side (Path I) or the unsubstituted side (Path II) to produce adsorbed alkoxide species. In Path I, a primary alkoxide was oxidized at the α-carbon to produce an aldehyde, which subsequently underwent decarbonylation to 2-pentenes. The primary alkoxide could also be protonated to give a primary alcohol which could desorb or form the final product 2-hexene. In Path II, a secondary alkoxide was oxidized to produce a ketone or was protonated to a secondary alcohol that was dehydrated to give 2-hexene. The active sites for the adsorption of 2-MTHP and O-intermediates were likely to be Ni sites.
On the Functional Group Tolerance of Ester Hydrogenation and Polyester Depolymerisation Catalysed by Ruthenium Complexes of Tridentate Aminophosphine Ligands
Fuentes, José A.,Smith, Samuel M.,Scharbert, M. Theresa,Carpenter, Ian,Cordes, David B.,Slawin, Alexandra M. Z.,Clarke, Matthew L.
supporting information, p. 10851 - 10869 (2015/07/20)
The synthesis of a range of phosphine-diamine, phosphine-amino-alcohol, and phosphine-amino-amide ligands and their ruthenium(II) complexes are reported. Five of these were characterised by X-ray crystallography. The activities of this collection of catalysts were initially compared for the hydrogenation of two model ester hydrogenations. Catalyst turnover frequencies up to 2400 h-1 were observed at 85 °C. However, turnover is slow at near ambient temperatures. By using a phosphine-diamine RuII complex, identified as the most active catalyst, a range of aromatic esters were reduced in high yield. The hydrogenation of alkene-, diene-, and alkyne-functionalised esters was also studied. Substrates with a remote, but reactive terminal alkene substituent could be reduced chemoselectively in the presence of 4-dimethylaminopyridine (DMAP) co-catalyst. The chemoselective reduction of the ester function in conjugated dienoate ethyl sorbate could deliver (2E,4E)-hexa-2,4-dien-1-ol, a precursor to leaf alcohol. The monounsaturated alcohol (E)-hex-4-en-1-ol was produced with reasonable selectivity, but complete chemoselectivity of C=O over the diene is elusive. High chemoselectivity for the reduction of an ester over an alkyne group was observed in the hydrogenation of an alkynoate for the first time. The catalysts were also active in the depolymerisation reduction of samples of waste poly(ethylene terephthalate) (PET) to produce benzene dimethanol. These depolymerisations were found to be poisoned by the ethylene glycol side product, although good yields could still be achieved. A simple catalyst for difficult reductions: Ruthenium complexes of P,N,N and P,N,O ligands catalyse the reduction of esters with high activities. The Ru complex of a phosphine-diamine ligand (see scheme) has been found to be a good catalyst for reducing alkene-, diene-, and alkyne-functionalised esters, displaying good activity and chemoselectivity. This catalyst was also active in the hydrogenation of waste poly(ethylene terephthalate) (PET).
Alkene isomerisation catalysed by a ruthenium PNN pincer complex
Perdriau, Sébastien,Chang, Mu-Chieh,Otten, Edwin,Heeres, Hero J.,De Vries, Johannes G.
supporting information, p. 15434 - 15442 (2016/02/18)
The [Ru(CO)H(PNN)] pincer complex based on a dearomatised PNN ligand (PNN: 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) was examined for its ability to isomerise alkenes. The isomerisation reaction proceeded under mild conditions after activation of the complex with alcohols. Variable-temperature (VT) NMR experiments to investigate the role of the alcohol in the mechanism lend credence to the hypothesis that the first step involves the formation of a rearomatised alkoxide complex. In this complex, the hemilabile diethylamino side-arm can dissociate, allowing alkene binding cis to the hydride, enabling insertion of the alkene into the metal-hydride bond, whereas in the parent complex only trans binding is possible. During this study, a new uncommon Ru0 coordination complex was also characterised. The scope of the alkene isomerisation reaction was examined. The catalyst tested positive! A dearomatised ruthenium PNN (2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) pincer complex, [Ru(CO)H(PNN)], was evaluated as an alkene isomerisation catalyst. The isomerisation reaction was greatly accelerated by the addition of alcohols, in particular isopropanol. Isomerisation of terminal to internal alkenes took place at room temperature. A mechanism was proposed based on variable-temperature NMR spectroscopy.
Highly functionalized and potent antiviral cyclopentane derivatives formed by a tandem process consisting of organometallic, transition-metal-catalyzed, and radical reaction steps
Jagtap, Pratap R.,Ford, Leigh,Deister, Elmar,Pohl, Radek,Cisarova, Ivana,Hodek, Jan,Weber, Jan,Mackman, Richard,Bahador, Gina,Jahn, Ullrich
supporting information, p. 10298 - 10304 (2014/08/18)
A simple modular tandem approach to multiply substituted cyclopentane derivatives is reported, which succeeds by joining organometallic addition, conjugate addition, radical cyclization, and oxygenation steps. The key steps enabling this tandem process are the thus far rarely used isomerization of allylic alkoxides to enolates and single-electron transfer to merge the organometallic step with the radical and oxygenation chemistry. This controlled lineup of multiple electronically contrasting reactive intermediates provides versatile access to highly functionalized cyclopentane derivatives from very simple and readily available commodity precursors. The antiviral activity of the synthesized compounds was screened and a number of compounds showed potent activity against hepatitisC and dengue viruses.
