6434-77-1Relevant academic research and scientific papers
Photocatalytic Transfer Hydrogenolysis of Allylic Alcohols on Pd/TiO2: A Shortcut to (S)-(+)-Lavandulol
Takada, Yuki,Caner, Joaquim,Kaliyamoorthy, Selvam,Naka, Hiroshi,Saito, Susumu
supporting information, p. 18025 - 18032 (2017/12/08)
We report herein a regio- and stereoselective photocatalytic hydrogenolysis of allylic alcohols to form unsaturated hydrocarbons employing a palladium(II)-loaded titanium oxide; the reaction proceeds at room temperature under light irradiation without stoichiometric generation of salt wastes. Olefin and saturated alcohol moieties tolerated the reaction conditions. Hydrogen atoms were selectively incorporated into less sterically congested carbons of the allylic functionalities. This protocol allowed a short-step synthesis of (S)-(+)-lavandulol from (R)-(?)-carvone by avoiding otherwise necessary protection/deprotection steps.
METHOD FOR PRODUCING ORGANIC COMPOUND
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Paragraph 0113-0115, (2018/10/16)
PROBLEM TO BE SOLVED: To provide a method of subjecting a compound having on one carbon atom a carbon atom constituting a carbon-carbon double bond and a functional group such as a hydroxyl group to a reductive reaction condition and producing an organic compound having the functional group substituted with a hydrogen atom. SOLUTION: There is provided a method for producing a compound represented by a formula (50) from a raw material compound represented by a formula (10). The method includes a step of irradiating a reaction system with light, the reaction system comprising the raw material compound, a hydrogen source compound, and a catalyst having a palladium component supported by a carrier containing titanium oxide. (R11 to R15 are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a cyclic structure or a derivative group thereof, or a heteroatom-containing group having 1 to 20 carbon atoms which may have a cyclic structure or a derivative group thereof; and R16 is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or an acyl group having 1 to 20 carbon atoms which may have a cyclic structure, or -CH(CH2OH)2).) COPYRIGHT: (C)2015,JPO&INPIT
A Bridged Tetrahydrophosphole Ylide Derived from 9-Phenylphosphabicyclononane: A Reagent for E-Selective Wittig Reactions
Vedejs, E.,Peterson, M. J.
, p. 1985 - 1986 (2007/10/02)
The bicyclic ylide 4 reacts with aldehydes to afford the E-alkenes.Selectivity is 94 - 6percent E for unbranched aldehydes, but the selectivity decreases with increasing α-branching.Ylide 4 is the first E-selective, nonstabilized ylide that allows efficient utilization of the P-alkyl substituent.
An Unprecedented Intramolecular Migration of Carbon Groups from Aluminum to an Adjacent Vinylic Center and Its Application to the Synthesis of Stereodefined Olefins
Miller, Joseph A.
, p. 998 - 1000 (2007/10/02)
Hydroalumination of 1-chloro-1-alkynes by sodium trialkylaluminum hydrides furnishes stereo- and regioselectively the respective (E)-1-chloro-1-alkenylalanates, which, in the presence of NaOMe, undergo a novel 1,2-migration of a carbon group from Al to the adjacent vinylic center to generate a useful synthesis of di- and trisubstituted olefins of defined geometry.
Regioselective Synthesis of Therminal Olefins from Alkanes via Rhodium-Catalyzed C-H Activation
Sakakura, Toshiyasu,Hayashi, Teruyuki,Tanaka, Masato
, p. 859 - 862 (2007/10/02)
Pentane and decane were regioselectively transformed into 1-butene and 1-nonene with the simultaneous formation of acetaldehyde by photocatalysis in the presence of RhCl(CO)(PMe3)2 under carbon monoxide.
Syntheses a l'aide de sulfones. XVIII. Utilisation des disulfones-1,1 pour la synthese stereoselective de composes olefiniques
Cuvigny, Therese,Penhoat, Catherine Herve Du,Julia, Marc
, p. 43 - 51 (2007/10/02)
2-Alkenyl-1,1-disulfones 4 are readily available in excellent yields by condensation of aldehydes with bisaryl or bisalkylsulfonylmethanes in the presence of piperidine acetate and molecular sieves at room temperature.A small amount of the 1-alkenyl isomer is also found when the aldehyde is α-substituted but it can be converted into the 2-alkenyl isomer by base catalysed equilibration.The 2-alkenyl-1,1-disulfones display only E geometry whereas E allylic monosulfones are difficult to isolate in a state of stereochemical purity (about 20percent of the Z isomer at equilibrium (8)).Alkylation is readily performed: treatment of 4 and 6 by sodium hydride in dimethylformamide and then by methyl iodide gives disulfones 5 E and 7 in 78-95percent yields.The alkylation of 4 (R=Et) by butyl iodide gives 70percent of 5 E(R=Et, R'=n-Bu) resulting from alkylation at the α position and 8percent of 3 (R=Et, R'=n-Bu) resulting from alkylation at the γ position.The α isomer is readily purified by crystallization.Reduction of disulfones 4 or 5 by aluminium amalgam leads quantitatively to allylic sulfones 2E or 8E.Olefins 9E are obtained upon total reduction of disulfones 4 or 5 by lithium in ethylamine at -78 deg C but in the case of disulfones 5 the olefins 9E are contaminated by isomers 10E and 10Z.
ORGANIC PHOTOCHEMISTRY WITH 6.7eV PHOTONS: DECOMPOSITION OF 1,1-DISUBSTITUTED CYCLOPROPANES IN SOLUTION
Srinivasan, R,Baum, Thomas,Ors, Jose A.
, p. 4795 - 4798 (2007/10/02)
The course of the two-bond cleavage reactions of cyclopropanes in photolysis at 185nm in solution is strikingly influenced by disubstitution of one of the carbons in the ring.
Stereoselectivity in the Cross-metathesis of Oct-1-ene and cis- or trans-Oct-2-ene
Uchida, Akira,Hinenoya, Masayoshi,Yamamoto, Toshihiko
, p. 1089 - 1092 (2007/10/02)
The yields and the initial ratios of cis and trans geometries of non-2-ene, tridec-6-ene, or tetradec-7-ene, formed by the cross-metathesis of oct-1-ene and cis- or trans-oct-2-ene catalyzed by tungsten hexachloride-tetraphenyltin (A), hexaphenoxytungsten-ethylaluminium dichloride (B), or tungsten hexachloride-triethylaluminium (C), have been correlated to the interactions of alkyl substituents on tungstacyclobutane.The results strongly suggest that the 2,4-interaction, between the alkyl substituent on C2 and the tungsten moiety, plays an important part in determining the distribution of products.
THE EFFECT OF CROWN ETHER ON STERIC HINDRANCE TO BASE APPROACH IN BIMOLECULAR ELIMINATION: EVIDENCE AGAINST CLUMP AGGREGATE MODEL OF ION-PAIRED ALKOXIDE BASE
Pankova, Magdalena,Zavada, Jiri
, p. 3150 - 3159 (2007/10/02)
The effect of 18-crown-6-ether upon geometrical orientation and rates was investigated in tert-C4H9OK-tert-C4H9OH promoted anti-elimination from two homologous series of tosylates, RCH2CHOTsC5H11 and RCHOTsCH2C5H11 (R = H, CH3, C2H5, n-C3H5, iso-C3H7, tert-C4H9).Steric requirements of the cis- and trans-stereoselective base species operating in the reaction in the absence and in the presence of the crown ether, respectively, have been assessed.An unambiguous distinction has been made between two pending models of the cis-stereoselective (ion-paired) base.
