65995-76-8Relevant academic research and scientific papers
Indium-mediated allylation of carbonyl compounds in deep eutectic solvents
González-Gallardo, Nerea,Saavedra, Beatriz,Guillena, Gabriela,Ramón, Diego J.
, (2021/08/26)
This study describes, for the first time, the in situ generation of indium organometallic reagents in environmentally friendly deep eutectic solvents (DESs). The allylation process of different carbonyl compounds is achieved mediated by indium metal and u
A Mechanochemical Zinc-Mediated Barbier-Type Allylation Reaction under Ball-Milling Conditions
Yin, JieXiang,Stark, Roderick T.,Fallis, Ian A.,Browne, Duncan L.
, p. 2347 - 2354 (2020/02/04)
A ball-milling-enabled zinc-mediated Barbier-type allylation reaction is reported. Notably, running the reaction in this manner renders it effective irrespective of the initial morphology of the zinc metal. The process is operationally simple, does not re
Chemo-Enzymatic Oxidative Rearrangement of Tertiary Allylic Alcohols: Synthetic Application and Integration into a Cascade Process
Brenna, Elisabetta,Crotti, Michele,De Pieri, Matteo,Gatti, Francesco G.,Manenti, Gabriele,Monti, Daniela
supporting information, p. 3677 - 3686 (2018/06/04)
A chemo-enzymatic catalytic system, comprised of Bobbitt's salt and laccase from Trametes versicolor, allowed the [1,3]-oxidative rearrangement of endocyclic allylic tertiary alcohols into the corresponding enones under an Oxygen atmosphere in aqueous media. The yields were in most cases quantitative, especially for the cyclopent-2-en-1-ol or the cyclohex-2-en-1-ol substrates without an electron withdrawing group (EWG) on the side chain. Transpositions of macrocyclic alkenols or tertiary alcohols bearing an EWG on the side chain were instead carried out in acetonitrile by using an immobilized laccase preparation. Dehydro-Jasmone, dehydro-Hedione, dehydro-Muscone and other fragrance precursors were directly prepared with this procedure, while a synthetic route was developed to easily transform a cyclopentenone derivative into trans-Magnolione and dehydro-Magnolione. The rearrangement of exocyclic allylic alcohols was tested as well, and a dynamic kinetic resolution was observed: α,β-unsaturated ketones with (E)-configuration and a high diastereomeric excess were synthesized. Finally, the 2,2,6,6-tetramethyl-1-piperidinium tetrafluoroborate (TEMPO+BF4?)/laccase catalysed oxidative rearrangement was combined with the ene-reductase/alcohol dehydrogenase cascade process in a one-pot three-step synthesis of cis or trans 3-methylcyclohexan-1-ol, in both cases with a high optical purity. (Figure presented.).
Chemoenzymatic route to various spirocyclic compounds based on enantiomerically enriched tertiary allylic, homoallylic, and homopropargylic alcohols
Tanyeli, Cihangir,Oezdemirhan, Devrim
, p. 658 - 666 (2014/05/20)
A ring closing metathesis (RCM) reaction of dienes and an intramolecular Pauson-Khand (PKR) reaction of enynes derived from tertiary allyl, homoallyl, and homopropargyl alcohol backbones to afford the corresponding spirocyclic dihydrofuran and dihydropyra
Cooperative titanocene and phosphine catalysis: Accelerated C-X activation for the generation of reactive organometallics
Fleury, Lauren M.,Kosal, Andrew D.,Masters, James T.,Ashfeld, Brandon L.
, p. 253 - 269 (2013/03/14)
The study presented herein describes a reductive transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields up to 99%. It was discovered that phosphine ligands effectively accelerate the reductive transmetalation event to enable the metalation of C-X bonds at temperatures as low as -40 °C. Performing the reactions in the presence of chiral diamines and amino alcohols led to the enantioselective allylation of aldehydes.
Mild and efficient barbier allylation reaction mediated by magnesium powder under solvent-free conditions
Li, Shunxi,Wang, Jin-Xian,Wen, Xiaoliu,Ma, Xiaofang
experimental part, p. 849 - 855 (2011/03/19)
A novel and highly efficient synthesis of homoallylic alcohols is achieved by the allylation of carbonyl compounds using magnesium powder as mediator under solvent-free conditions. A series of aldehydes and ketones are converted to the corresponding homoa
Generation of allyl Grignard reagents via titanocene-catalyzed activation of allyl halides
Fleury, Lauren M.,Ashfeld, Brandon L.
scheme or table, p. 2427 - 2430 (2010/07/04)
A protocol for the generation of allyl Grignard reagents via the catalytic activation of allyl halides is described herein. Subsequent nucleophilic addition to carbonyl derivatives provided the desired homo allylic alcohols in excellent yields (84-99%). E
Catalytic use of a soluble organoindium(III) species for allylation and crotylation of ketones with boronates
Yamaguchi, Miyuki,Morita, Naohide,Schneider, Uwe,Kobayashi, Shu
experimental part, p. 1461 - 1465 (2010/08/20)
The unprecedented use of a soluble organoindium species, indium(III) hexamethyldisilazide [In(III)(hmds)3], for catalytic carbon-carbon bond formations between ketones and boronates, is reported. Various functionalized tertiary homoallyl alcoho
The solvent-free addition reaction of allylzinc bromide and carbony compounds
Zhang, Yumei,Jia, Xuefeng,Wang, Jin-Xian
experimental part, p. 2983 - 2986 (2009/11/30)
The reactivity of organozincs could be enhanced dramatically under solvent-free conditions. Allylzinc bromide can react rapidly with aldehydes and ketones to give homoallylic alcohols in high yields in the absence of a catalyst under sol vent-free conditions in an open atmosphere at room temperature. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
Stereoselective aziridination of cyclic allylic alcohols using chloramine-T
Coote, Susannah C.,O'Brien, Peter,Whitwood, Adrian C.
supporting information; experimental part, p. 4299 - 4314 (2009/02/07)
The stereoselective aziridination of a range of cyclic allylic alcohols using two different chloramine salts (4-MeC6H4SO 2NClNa, TsNClNa and t-BuSO2NClNa, BusNClNa) has been explored. The stereoselectivity of these reactions was highly dependent on the structure of the allylic alcohol and the chloramine salt. Generally, mixtures of cis- and trans-hydroxy aziridines were obtained, in which the major diastereomer was the cis-hydroxy aziridine, whilst complete cis- diastereoselectivity was observed in the aziridination of 1,3-disubstituted allylic alcohols. In each case studied, aziridination using BusNClNa gave higher cis-stereoselectivity than that observed for the same reaction using TsNClNa. Unexpectedly, application of the aziridination conditions to 1-substituted cyclopen-2-en-1-ols did not generate the aziridines. Instead, epoxy sulfonamides were obtained.
