138662-72-3Relevant academic research and scientific papers
Preparation of a new MOP ligand containing a long-chain alkyl group and its use for palladium-catalyzed asymmetric hydrosilylation of cyclic 1,3-dienes
Han, Jin Wook,Hayashi, Tamio
, p. 976 - 977 (2001)
A new MOP ligand containing n-octyl group at 6 and 6′ positions of (R)-2-(diphenylphosphino)-2′-aryl-1,1′-binaphthyl skeleton was prepared and used for palladium-catalyzed asymmetric hydrosilylation of cyclic 1,3-dienes with trichlorosilane. By introducti
Active antimony mediated reaction of 3-bromocyclohexene with aldehydes
Jin, Qi-Hui,Ren, Ping-Da,Li, Yu-Qiong,Yao, Zi-Peng
, p. 4151 - 4156 (1998)
Active antimony in situ from reduction of SbCl3 by Zn powder mediated reaction of 3-bromocyclohexene with aldehydes. The reaction has high chemo- and good stereo-selectivity.
Asymmetric hydrosilylation of cyclohexa-1,3-diene with trichlorosilane by palladium catalysts coordinated with chiral phosphoramidite ligands
Park, Hoon Seo,Han, Jin Wook,Shintani, Ryo,Hayashi, Tamio
, p. 418 - 420 (2013)
Chiral phosphoramidite ligands prepared from (S)-binaphthol and various secondary amines were examined for the palladium-catalyzed asymmetric hydrosilylation of cyclohexa-1,3-diene with trichlorosilane. With a sterically demanding phosphoramidite bearing bis(diphenylmethyl)amine, the high enantiomeric excess of 87% was achieved, which is the highest enantioselectivity in the hydrosilylation of cyclohexadiene reported to date. The catalytic activity in the present hydrosilylation was high with all of the ligands employed, while the enantioselectivities varied dramatically depending on the dialkylamine moiety of the phosphoramidite ligand.
Diastereoselective reaction of aldehydes with 3-bromocyclohexene and tin
Zhou,Chen,Wu
, p. 2661 - 2664 (1994)
The reaction of 3-bromocyclohexane and powdered tin with aromatic aldehydes and an alkynal provides excellent erythro-selective products, while the corresponding reactions with aliphatic aldehydes proceed with moderate erythroselectivity.
Kinetic Resolution of Secondary Allyl Boronates and Their Application in the Synthesis of Homoallylic Amines
Villar, Laura,Orlov, Nikolai V.,Kondratyev, Nikolay S.,Uria, Uxue,Vicario, Jose L.,Malkov, Andrei V.
, p. 16262 - 16265 (2018)
Highly enantioenriched, chromatographically-stable secondary allyl boronates featuring a 1,1,2,2-tetraethyl-1,2-ethanediol fragment (Epin) were obtained by kinetic resolution of their racemic mixtures. The Epin group at boron considerably improved stability of allyl boronates allowing them to be readily isolated by chromatography on silica. The resolved reagents were applied in stereoselective synthesis of homoallylic amines with an internal double bond employing unprotected imines formed in situ from aldehydes and ammonia. The reactions proceeded with an excellent transfer of chirality.
Zirconocenes vs. Alanes: A Crucial Choice of the Allyl Source for Highly Diastereoselective Allylzincation of Nonracemic Chiral Imines
Coffinet, Michael,Jaroschik, Florian,Vasse, Jean-Luc
, p. 2319 - 2327 (2016)
An efficient in-situ generation of allylzinc compounds from allylzirconocenes applied to the allylmetallation of phenylglycinol-derived imines is described. The key advantage of the method lies in the concomitant formation of a zirconocene during the Zr-Zn transmetallation step, which appears to be beneficial for the stereoselectivity of the reaction. In the specific case of coupling of imines with racemic chiral allylzinc compounds, this method provides highly diastereoselective access to valuable enantiomerically enriched amines with high synthetic potential. The influence of the allylmetal source (allylalanes vs. allylzirconocenes) on the allylzinc formation was investigated during allylzincation of phenylglycinol-derived imines. Concomitant formation of zirconocene along with the allylzinc species enables the allylzirconocenes to induce higher diastereoselectivities, thus providing a general method for the synthesis of homoallylic amines.
Titanium-catalyzed hydroalumination of conjugated dienes: Access to fulvene-derived allylaluminium reagents and their diastereoselective reactions with carbonyl compounds
Joseph, Jomy,Jaroschik, Florian,Harakat, Dominique,Radhakrishnan,Vasse, Jean-Luc,Szymoniak, Jan
, p. 5433 - 5438 (2014)
The described titanium-catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL-H) and a catalytic amount of [Cp 2TiCl2] (Cp=cyclopentadienyl). When applied to mono- and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react regio- and stereoselectively with both aldehydes and ketones to afford homoallylic alcohols that are suitable synthons for functionalized cyclopentanones. An extension of this methodology to simple dienes was also investigated. In the proposed mechanism, the initially formed bimetallic species (Ti/Al) are involved in the two possible catalytic cycles with a direct hydroalumination or/and a hydrotitanation followed by a titanium to aluminium transmetallation. Aluminate your chemistry! The described titanium-catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminum reagents. When applied to mono- and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner producing allylaluminium compounds that react with aldehydes and ketones to afford homoallylic alcohols (see scheme; DIBAL-H=diisobutylaluminium hydride, Cp=cyclopentadienyl).
(+)-Camphor-mediated kinetic resolution of allylalanes: a strategy towards enantio-enriched cyclohex-2-en-1-ylalane
Coffinet, Micha?l,Massicot, Fabien,Joseph, Jomy,Behr, Jean-Bernard,Jaroschik, Florian,Vasse, Jean-Luc
, p. 111 - 114 (2017)
An efficient (+)-camphor-mediated kinetic resolution of racemic cyclohex-2-en-1-ylalane is described. This approach provides an enantiomerically enriched form of the alane, in situ available for synthetic uses. Applied to the allylation of aldehydes, this protocol leads to the corresponding homoallylalcohols in a highly enantioselective manner.
Iridium-catalyzed C-C coupling via transfer hydrogenation: Carbonyl addition from the alcohol or aldehyde oxidation level employing 1,3-cyclohexadiene
Bower, John F.,Patman, Ryan L.,Krische, Michael J.
, p. 1033 - 1035 (2008)
Under hydrogen autotransfer conditions employing a catalyst derived from [lr(cod)CI]2 and BIPHEP, 1,3-cyclohexadiene (CHD) couples to benzylic alcohols 1a-9a to furnish carbonyl addition products 1c-9c, which appear as single diastereomers with variable quantities of regioisomeric adducts 1d-9d. Under related transfer hydrogenation conditions employing isopropanol as terminal reductant, identical carbonyl adducts 1c-9c are obtained from the aldehyde oxidation level. Isotopic labeling studies corroborate a mechanism involving hydrogen donation from the reactant alcohol or sacrificial alcohol (i-PrOH).
Indium-mediated, highly efficient and diastereoselective addition of cyclic secondary allylic bromides to carbonyl compounds
Khan, Faiz Ahmed,Prabhudas
, p. 7595 - 7599 (2000)
Indium-mediated addition of 3-bromocyclohexene and 3-bromocyclooctene to a variety of aromatic aldehydes and cyclohexanone proceeds smoothly with excellent syn diastereoselectivity to produce the corresponding cycloalkenyl substituted homoallylic alcohols in good to high yields. (C) 2000 Elsevier Science Ltd.
