131211-27-3Relevant academic research and scientific papers
CYCLOPENTADIENYL/ADAMANTYL PHOSPHINIMINE TITANIUM COMPLEXES
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, (2021/10/30)
Provided in this disclosure are titanium complexes that contain 1) a cyclopentadienyl ligand; 2) an adamantyl-phosphinimine ligand; and 3) at least one activatable ligand. The use of such a complex, in combination with an activator, as an olefin polymerization catalyst is demonstrated. The catalysts are effective for the copolymerization of ethylene with an alpha olefin (such as 1-butene, 1-hexene or 1-octene) and enable the production of high molecular weight copolymers (Mw greater than 25,000) at high productivity under solution polymerization conditions.
Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
, p. 1122 - 1128 (2020/03/03)
Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
A Bulky Three-Hindered Quadrant Bisphosphine Ligand: Synthesis and Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes
Sawatsugawa, Yuuki,Tamura, Ken,Sano, Natsuhiro,Imamoto, Tsuneo
supporting information, p. 8874 - 8878 (2019/11/03)
A bulky three-hindered quadrant bisphosphine ligand, di-1-adamantylphosphino(tert-butylmethylphosphino)methane, named BulkyP*, has been synthesized via a convergent short pathway with chromatography-free procedures. The ligand is a crystalline solid and can be readily handled in air. Its rhodium(I) complex exhibits very high enantioselectivities and catalytic activities in the asymmetric hydrogenation of functionalized alkenes.
Reductive Elimination to Form C(sp3)-N Bonds from Palladium(II) Primary Alkyl Complexes
Peacock, D. Matthew,Jiang, Quan,Cundari, Thomas R.,Hartwig, John F.
supporting information, p. 3243 - 3247 (2018/10/05)
Reductive eliminations to form alkyl-nitrogen bonds are rare, and examples of this reaction from isolated complexes containing simple, unstabilized primary alkyl groups have not been observed. We report the synthesis of stable neopentylpalladium(II) anilido and methyleneamido complexes that undergo reductive elimination to form the C(sp3)-N bonds in N-neopentyl anilines and N-neopentyl imines, respectively. The synthesis and isolation of these complexes were enabled by weak chelation of palladium by P,O ancillary ligands. DFT calculations suggest that neopentylpalladium(II) complexes undergo reductive elimination by a concerted mechanism resembling a migration of the alkyl ligand to the nitrogen either following initial dissociation of the oxygen donor or in concert with lengthening of the Pd-O bond, depending on the identities of the reacting and ancillary ligands.
Catalyst system
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, (2017/11/17)
The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine or stibine ligand, andc) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.
Expedient copper-free one-pot alkynylation-cyclization sequence for the preparation of 2-substituted 7-azaindoles
Lessing, Timo,Sterzenbach, Fabian,Müller, Thomas J. J.
supporting information, p. 1217 - 1221 (2015/06/02)
Abstract 2-Substituted 7-azaindoles are rapidly and efficiently prepared in a one-pot copper-free alkynylation-cyclization sequence starting from 2-aminopyridyl halides and terminal alkynes. Most importantly the amino nitrogen atom neither requires activation nor protection throughout the sequence.
General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
supporting information; experimental part, p. 9727 - 9732 (2012/07/14)
Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
Highly chemoselective metal-free reduction of phosphine oxides to phosphines
Li, Yuehui,Lu, Liang-Qiu,Das, Shoubhik,Pisiewicz, Sabine,Junge, Kathrin,Beller, Matthias
, p. 18325 - 18329 (2013/01/15)
Unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of catalytic amounts of specific Br?nsted acids. By utilizing inexpensive silanes, e.g., PMHS or (EtO)2MeSiH, other reducible functional groups such as ketones, aldehydes, olefins, nitriles, and esters are well-tolerated under optimized conditions.
Novel catalysts useful for catalyzing the coupling of arylhalides with arylboronic acids
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Page/Page column 5-6, (2008/06/13)
The present invention relates to a new method of cross-coupling aryl moieties comprising reacting an arylhalide with an arylboronic acid in the presence of a palladium compound and a compound comprising a di-alkylphosphine moiety.
Production of novel phosphane ligands and use in catalytical reactions
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, (2008/06/13)
The invention relates to novel phosphane ligands of formula (Ia) and (Ib): (adamantyl)nP(alkyl)m(1a); (adamantyl)o(Alkyl)qP (alkylen′)P(adamantyl)r(alkyl)s (1b), wherein adamantyl represents an adamantyl radical (IIa, IIb) bonded to the phosphorous atom in position 1 or 2. The invention also relates to the production and use of the above-mentioned ligands in the presence of transitional metal compounds of the 8th. Subgroup of PSE for catalytic reactions, particularly for the refining of halogen aromatics for producing aryl olefins, dienes, diarylene, benzoic acid and acrylic acid derivatives, aryl alkanes and also amines.
