10405-85-3Relevant academic research and scientific papers
Reduction of alkyl and vinyl sulfonates using the CuCl2· 2H2O-Li-DTBB(cat.) system
Radivoy, Gabriel,Alonso, Francisco,Moglie, Yanina,Vitale, Cristian,Yus, Miguel
, p. 3859 - 3864 (2005)
The reduction of a series of alkyl mesylates, dimesylates and triflates to the corresponding hydrocarbons was efficiently performed using a reducing system composed of CuCl2·2H2O, an excess of lithium sand and a catalytic amount (5 mol%) of 4,4′-di-tert-butylbiphenyl (DTBB), in tetrahydrofuran at room temperature. The process was also applied to enol and dienol triflates affording alkenes and dienes, respectively. The use of the deuterated copper salt CuCl2·2D2O allowed the simple preparation of the corresponding deuterated products.
BASE-PROMOTED ELIMINATION OF HYDROGEN FLUORIDE FROM ALKYL FLUORIDES: REACTIVITY AND STEREOCHEMISTRY
Matsubara, Seijiro,Matsuda, Hiroyuki,Hamatani, Takeshi,Schlosser, Manfred
, p. 2855 - 2864 (1988)
- The alcoholate-promoted dehydrohalogenation of 5-nonyl fluoride and cyclododecyl fluoride, typical straight-chain and, respectively, medium-size cyclic substrates, leads to cis- and trans-alkenes in an approximate ratio of 1:3.With bulky bases such as lithium diisopropylamide the trans isomer may be obtained almost exclusively.In general, the elimination of hydrogen fluoride proceeds very slowly.Increase of the base strength has only a moderate effect on the rates.Electrophilic assistance as provided by lithium cations in media of low polarity can, however, considerably accelerate the reaction. - Cyclododecyl fluoride cannot be prepared from cyclododecanol.It is, however, readily accessible by bromofluorination of cyclododecene and subsequent reduction of the adduct with stannane.
VACUUM FLASH PYROLYSIS (VFP) OF MALONYL PEROXIDES: DECARBOXYLATION VERSUS DECARBONYLATION OF THE INTERMEDIARY α-LACTONES
Adam, Waldemar,Cadiz, Carlos,Mazenod, Francois
, p. 1203 - 1206 (1981)
Vacuum Flash Pyrolysis (VFP) at ca. 450-500 deg C and ca. 0.1-0.3 Torr of spirocyclic malonyl peroxides (2a,b) affords high yields of allenes (5a,b), while the simple malonyl peroxide (2c) leads to ketone (4), derived respectively from decarboxylation of the intermediary α-lactones (3).
PALLADIUM COMPLEXES OF PHOSPHORUS ACID DISUBSTITUTED ETHERS. SYNTHESIS, STRUCTURE, CATALYSIS
Nifant'ev, E. E.,Kukhareva, T. S.,Antipin, M. Yu.,Struchkov, Yu. T.,Klabunovsky, E. I.
, p. 797 - 803 (1983)
Complexes of the type of have been prepared by the reaction of bis-(?-allylpalladiumchloride) with phosphorous acid disubstituted ethers; their structure has been studied by IR- and NMR- spectroscopy and X-ray analysis.The complexes have a dimeric centro-symmetric structure which is usual for bivalent palladium compounds with a slightly distorted flat-square coordination of the central atom.These compounds are active catalysts for hydrogenation of unsaturated compounds.Complexes of biphosphites of sugars can impart asymmetry in hydrogenation of prochiral substrates.
Boosting the Metathesis Activity of Molybdenum Oxo Alkylidenes by Tuning the Anionic Ligand σ Donation
De Jesus Silva, Jordan,Pucino, Margherita,Zhai, Feng,Mance, Deni,Berkson, Zachariah J.,Nater, Darryl F.,Hoveyda, Amir H.,Copéret, Christophe,Schrock, Richard R.
, p. 6875 - 6880 (2021)
The catalytic performances of molecular and silica-supported molybdenum oxo alkylidene species bearing anionic O ligands [ORF9, OTPP, OHMT - where ORF9 = OC(CF3)3, OTPP = 2,3,5,6-tetraphenylphenoxy, OHMT = hexamethylterphenoxy] with different σ-donation a
High yield of liquid range olefins obtained by converting i-propanol over zeolite H-ZSM-5
Mentzel, Uffe V.,Shunmugavel, Saravanamurugan,Hruby, Sarah L.,Christensen, Claus H.,Holm, Martin S.
experimental part, p. 17009 - 17013 (2010/03/23)
Methanol, ethanol, and i-propanol were converted under methanol-to-gasoline (MTH)-like conditions (400°C, 1-20 bar) over zeolite H-ZSM-5. For methanol and ethanol, the catalyst lifetimes and conversion capacities are comparable, but when i-propanol is use
Radical Addition of N-Chlorophthalimide and N-Bromophthalimide to Alkenes
Kirsch, Andre,Luening, Ulrich
, p. 129 - 134 (2007/10/03)
The addition of N-chlorophthalimide (1b) to alkenes 3 via phthalimidyl radicals introduces a chlorine atom and an imidyl moiety to vicinal C-atoms of a carbon chain. The yields depend on the substituents of the alkene 3. The regioselectivity can be explained by steric and electronic effects; differences in the behavior of the addition of N-chlorophthalimide (1b) and N-bromophthalimide (1a) can be explained by a reversible attack of the phthalimidyl radical to the double bond.
Reductive Deoxygenation of Ketones and Secondary Alcohols by Organoaluminum Lewis Acids
Eisch, John J.,Liu, Zhi-Rong,Boleslawski, Marek P.
, p. 2143 - 2147 (2007/10/02)
The reductive deoxygenation of ketones and secondary alcohols to the corresponding methylene hydrocarbons has been achieved in good to excellent yield by the combined action of an aluminum hydride source and a strongly Lewis-acidic aluminum reagent.Such reductions were successful with diaryl ketones, alkyl aryl ketones, and dialkyl ketones, as exemplified by the reduction of benzophenone, acetophenone and 5-nonanone, respectively.The corrresponding secondary alcohols of these ketones, namely benzhydrol, 1-phenyl-1-ethanol, and 5-nonanol, could also be converted into their respective methylene hydrocarbons by Lewis-acidic sources of aluminum hydride.All such reductions of ketones could be conducted in a single reaction flask in a one-, two-, or three-step process.In the one-step process, which is most suitable for diaryl ketones, i-BuAlCl2 may be employed as both the hydride source and the Lewis acid.For alkyl aryl ketones a two-step process, consisting first of reduction with i-Bu2AlH and then treatment with AlBr3 (with or without catalysis of Cp2TiCl2), leads to better yields.Finally, for dialkyl ketones a three-step process proved to be preferred, wherein a sequential treatment with i-Bu2AlH, AlBr3 and then additional i-Bu2AlH (with a Ni(acac)2 catalyst) gives the highest conversion to alkane.If required, residual alkene may be removed by a brief catalytic hydrogenation or treatment with BH3THF.The ease of deoxygenating the foregoing ketones and secondary alcohols appears to be governed by the ease of forming, and the relative stability of, the corresponding carbenium ion intermediates, namely Ar2HC+ > ArRHC+ > R2HC+.The driving force for such deoxygenations by these aluminum reagents undoubtedly is the exothermic formation of the dialuminoxane system, R2Al-O-AlR2.
Hydroboration. 86. Convenient Conversion of Aldehydes and Ketones into the Corresponding Alkenes via Hydroboration of their Enamines. A Remarkably Simple Synthesis of Either (Z)- or (E)-Alkenes
Singaram, Bakthan,Rangaishenvi, Milind V.,Brown, Herbert C.,Goralski, Christian G.,Hasha, Dennis L.
, p. 1543 - 1549 (2007/10/02)
Aldehydes and ketones are converted into the corresponding alkenes via hydroboration of their enamines.Hydroboration of aldehyde enamines by 9-borabicyclononane (9-BBN), followed by methanolysis, affords the corresponding terminal alkenes in 75-90percent yields.Unsaturated aldehyde enamines produce the corresponding dienes under these conditions.Enamines derived from substituted cyclic ketones and heterocyclic ketones are readily accommodated in this reaction to afford the corresponding alkenes in very good yields.The synthesis of pure (Z)- or (E)-alkenes is readily achieved from the same acyclic ketone enamine by modification of the hydroboration-elimination procedure: (A) hydroboration by 9-BBN followed by methanolysis or (B) hydroboration by borane methyl sulfide (BMS) followed by methanolysis and hydrogen peroxide oxidation.Mechanistic rationale is provided.
1,2-DIALKYLVINYLSILANES FROM α-SILYL EPOXIDES VIA ORGANOLITHIUM REAGENTS
Santiago, Braulio,Lopez, Carlos,Soderquist, John A.
, p. 3457 - 3460 (2007/10/02)
The reactions of cis-α-epoxysilanes (1) with an excess of alkyllithium reagents were found to cleanly provide 1,2-dialkylvinylsilanes (3).A model for this reductive alkylation is advanced which explains the role of substituents in determining the product stereochemistry.
