Chiral phosphine ligands

Yamamoto, Kosuke’s team published research in Organic Letters in 2016-10-07 | 152140-65-3

Organic Letters published new progress about Allylic alkylation catalysts, stereoselective. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide].

Yamamoto, Kosuke; Qureshi, Zafar; Tsoung, Jennifer; Pisella, Guillaume; Lautens, Mark published the artcile< Combining Ru-Catalyzed C-H Functionalization with Pd-Catalyzed Asymmetric Allylic Alkylation: Synthesis of 3-Allyl-3-aryl Oxindole Derivatives from Aryl α-Diazoamides>, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is ruthenium catalyst functionalization palladium asym allylic alkylation aryl diazoamide; allylaryl oxindole stereoselective preparation.

Ruthenium-catalyzed C-H functionalization was successfully combined with palladium-catalyzed asym. allylic alkylation in one pot. The novel dual-metal-catalyzed reaction provides a variety of 3-allyl-3-aryl oxindoles from the corresponding α-diazoamides in up to 99% yield with up to 85% ee. The appropriate ligand choice is important to promote the sequential reaction, avoiding undesired metal interaction or ligand exchange.

Referemce:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Araki, Tatsuya’s team published research in Synlett in 2011-03-01 | 139139-93-8

Synlett published new progress about Enantioselective synthesis. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Araki, Tatsuya; Hojo, Daiki; Noguchi, Keiichi; Tanaka, Ken published the artcile< Enantioselective synthesis of planar chiral paracyclophanes with short ansa chains and structure of strained dioxa[7]paracyclophane>, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is paracyclophane planar chiral stereoselective preparation.

The enantioselective synthesis of planar chiral [7] and [8]paracyclophanes has been achieved by the cationic rhodium(I)-(S)-H8-BINAP complex catalyzed [2+2+2] cycloaddition Planar chiral [9]paracyclophanes were also synthesized by the same method. The X-ray crystallog. anal. of the strained dioxa[7]paracyclophane revealed the significant deformation of the benzene ring from planarity.

Trost, Barry M’s team published research in Journal of the American Chemical Society in 2011-08-17 | 152140-65-3

Journal of the American Chemical Society published new progress about Allylic alcohols Role: RCT (Reactant), RACT (Reactant or Reagent) (esters). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Computed Properties of 152140-65-3.

Trost, Barry M.; Thaisrivongs, David A.; Hartwig, Jan published the artcile< Palladium-Catalyzed Asymmetric Allylic Alkylations of Polynitrogen-Containing Aromatic Heterocycles>, Computed Properties of 152140-65-3, the main research area is cyclohexenylmethyl nitrogen heterocycle enantioselective preparation; enantioselective allylic alkylation cyclohexenyl cyclopentenyl mesityl ester nitrogen heterocycle; trimethylbenzoate ester leaving group enantioselective allylic alkylation reaction.

Nonracemic cyclohexenylmethyl- and cyclopentenylmethyl-substituted nitrogen heterocycles such as I are prepared in 44-93% yields and in 75->99% ee by enantioselective allylic alkylation reactions of cyclohexenyl and cyclopentenyl trimethylbenzoates with methyl-substituted nitrogen heterocycles such as 2-methylpyrazine in the presence of bis(allylpalladium chloride) and a nonracemic dibenzamidodibenzobicyclooctane ligand. Methylated nitrogen-containing aromatic heterocycles such as 2-methylpyrazine, 2-methylpyrimidine, 3-methyl-6-phenylpyridazine, 2-methylquinoxaline, and 1-benzyl-2-methylbenzimidazole are effective reactants. 5,6,7,8-Tetrahydroquinoxaline also undergoes enantioselective allylic alkylation with a cyclohexenyl trimethylbenzoate to give cyclohexenyl tetrahydroquinoxaline II in 99% yield, >99% ee, and in 81:19 diastereoselectivity. The mesityl ester, whose steric bulk prevents competitive deacylation of the electrophile from “”hard”” nucleophiles, is introduced as a new leaving group in allylic alkylation chem. In contrast to previous studies of enantioselective allylic alkylation reactions with pyridine-based substrates, no precomplexation with a Lewis acid is required before deprotonation of the nucleophiles with LiHMDS, underscoring the relative acidity of these electron-deficient nucleophiles.

Yoshida, Mariko’s team published research in Tetrahedron: Asymmetry in 2012-06-30 | 325168-88-5

Tetrahedron: Asymmetry published new progress about Allylic alkylation. 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Computed Properties of 325168-88-5.

Yoshida, Mariko; Nemoto, Tetsuhiro; Zhao, Zengduo; Ishige, Yuta; Hamada, Yasumasa published the artcile< Enantioselective construction of all-carbon quaternary spirocenters through a Pd-catalyzed asymmetric intramolecular ipso-Friedel-Crafts allylic alkylation of phenols>, Computed Properties of 325168-88-5, the main research area is spirocyclohexadienone enantioselective synthesis; phenol Friedel Crafts allylic alkylation chiral ligand Pd catalyst.

A novel catalytic asym. synthetic method for making spirocyclohexadienones e. g., I with an all-carbon quaternary spirocenter was developed based on the Pd-catalyzed intramol. ipso-Friedel-Crafts allylic alkylation of phenols. When 5 mol % of the Pd catalyst and 12 mol % of (-)-9-NapBN (-) were used, the spirocyclic adduct was obtained with up to 93% ee, albeit with low chem. yield. On the other hand, when using 6 mol% of the Trost ligand (R,R), the spirocyclic adducts were obtained in good yields with up to 89% ee (diastereoselectivity = 9.2:1).

Shibata, Takanori’s team published research in Organic Letters in 2005-10-27 | 139139-93-8

Organic Letters published new progress about Alkenynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, COA of Formula: C44H40P2.

Shibata, Takanori; Arai, Yoshikazu; Tahara, Yuki published the artcile< Enantioselective Construction of Quaternary Carbon Centers by Catalytic [2 + 2 + 2] Cycloaddition of 1,6-Enynes and Alkynes>, COA of Formula: C44H40P2, the main research area is bicyclic cyclohexadiene quaternary carbon stereocenter preparation; enyne alkyne enantioselective cycloaddition chiral rhodium catalysis.

The enantioselective [2 + 2 + 2] cycloaddition of 1,6-enynes and alkynes using chiral rhodium catalysts gave cycloadducts containing quaternary carbon stereocenters. Both sym. and unsym. alkynes and acetylene could be used as coupling partners, and the corresponding bicyclic cyclohexa-1,3-dienes were obtained in good to excellent ee.

Tian, Sicong’s team published research in Molecular Nutrition & Food Research in 2021-07-31 | 606-68-8

Molecular Nutrition & Food Research published new progress about Endoplasmic reticulum. 606-68-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C21H27N7Na2O14P2, Product Details of C21H27N7Na2O14P2.

Tian, Sicong; Lei, Peng; Zhang, Jing; Sun, Yao; Li, Baolong; Shan, Yujuan published the artcile< Sulforaphane Balances Ca2+ Homeostasis Injured by Excessive Fat via Mitochondria-Associated Membrane (MAM)>, Product Details of C21H27N7Na2O14P2, the main research area is sulforaphane homeostasis fat mitochondria associated membrane; Ca2+ homeostasis; lipid metabolism; mitochondria function; mitochondria-associated membrane; sulforaphane.

Mitochondria-associated membrane (MAM) connects endoplasmic reticulum (ER) and mitochondria plays a significant role in lipid metabolism and Ca2+ homeostasis. Albeit sulforaphane (SFN) shows potential in ameliorating excessive fat accumulation and mitochondrial function; whether MAM is a target of SFN and its underlying mechanisms are still unclear. High-fat-intake models are established both in vivo and in vitro. SFN widens the distance between ER and mitochondria and down-regulates MAM tether protein mitofusin-2. SFN reverses the increase of Ca2+ induced by fatty acid and inhibits the Ca2+ channel inositol-1,4,5-trisphosphate receptor (IP3R). Compared with high fat group, SFN alleviates Ca2+ overload in the mitochondria and suppresses mitochondrial calcium uniporter (MCU). Furthermore, SFN increases mitochondrial DNA quantities and mitochondria membrane potential, while decreasing reactive oxygen species (ROS) production Finally, SFN increases mitochondria complexes IV content and ATP synthesis. These results suggest that SFN balances the Ca2+ homeostasis in the MAM through regulating Ca2+ flux by Ca2+ channel IP3R and MCU.

Miyauchi, Yuta’s team published research in Organic Letters in 2012-12-07 | 139139-86-9

Organic Letters published new progress about [4+2] Cycloaddition reaction (stereoselective). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application In Synthesis of 139139-86-9.

Miyauchi, Yuta; Noguchi, Keiichi; Tanaka, Ken published the artcile< Rhodium-Catalyzed One-Pot Intermolecular [2 + 2 + 2] Trimerization/Asymmetric Intramolecular [4 + 2] Cycloaddition of Two Aryl Ethynyl Ethers and 5-Alkynals>, Application In Synthesis of 139139-86-9, the main research area is rhodium catalyst trimerization asym cycloaddition aryl ethynyl ether alkynal; cyclohexadiene annulated enantioselective regioselective synthesis.

It has been established that a cationic Rh(I)/(R)-H8-BINAP complex catalyzes the one-pot intermol. [2+2+2] trimerization/asym. intramol. [4+2] cycloaddition of two aryl ethynyl ethers and 5-alkynals to produce annulated 1,4-cyclohexadienes possessing two stereogenic centers. E.g., rhodium-catalyzed reaction of 2-(ethynyloxy)naphthalene and MeCCCH2NTsCH2CHO gave 64% annulated 1,4-cyclohexadiene derivative (I).

Trost, Barry M’s team published research in Angewandte Chemie, International Edition in 2012 | 152140-65-3

Angewandte Chemie, International Edition published new progress about Decarboxylation (stereoselective). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, COA of Formula: C54H42N2O2P2.

Trost, Barry M.; Michaelis, David J.; Charpentier, Julie; Xu, Jiayi published the artcile< Palladium-Catalyzed Allylic Alkylation of Carboxylic Acid Derivatives: N-Acyloxazolinones as Ester Enolate Equivalents>, COA of Formula: C54H42N2O2P2, the main research area is acylbenzoxazolinone allylic enol carbonate stereoselective preparation enantioselective rearrangement decarboxylation; alkenoyl benzoxazolinone enantioselective preparation; enantioselective rearrangement decarboxylation acylbenzoxazolinone allylic enol carbonate palladium phosphinylbenzamide.

Acylbenzoxazolinone allylic enol carbonates I [R = Me, Et, EtCH2, H2C:CHCH2, PhCH2, cyclohexyl, Cl(CH2)3, EtO2C(CH2)3, TBDPSO(CH2)3; R1 = H2C:CHCH2, H2C:CMeCH2, H2C:C(SiMe3)CH2, 2-cyclohexen-1-yl, (E)-PhCH:CHCH2; TBDPS = tert-butyldiphenylsilyl] underwent stereoselective rearrangement and decarboxylation in the presence of the nonracemic phosphinylbenzamide II (R2 = 2-MeC6H4) and tris(dibenzylidene)dipalladium chloroform solvate to give nonracemic alkanoyl benzoxazolinones III in 58-99% yields and in 79-99% ee [R = Me, Et, EtCH2, H2C:CHCH2, PhCH2, cyclohexyl, Cl(CH2)3, EtO2C(CH2)3, TBDPSO(CH2)3; R1 = H2C:CHCH2, H2C:CMeCH2, H2C:C(SiMe3)CH2, 2-cyclohexen-1-yl, (E)-PhCH:CHCH2 with minor regioisomeric impurities formed when R1 = (E)-PhCH:CHCH2]. III (R = Me; R1 = 2-methyl-2-propenyl) in 97% ee was converted stereoselectively to carboxylic acid and alc. derivatives (S)-R2CHMeCH2CMe:CH2 (R2 = HO2C, PhCH2OCO, PhCH2SCO, HOCH2) in 78-86% yields and with the products in 96-97% ee.

Sarcher, Christian’s team published research in European Journal of Inorganic Chemistry in 2012 | 325168-88-5

European Journal of Inorganic Chemistry published new progress about Alkynes Role: RCT (Reactant), RACT (Reactant or Reagent). 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Electric Literature of 325168-88-5.

Sarcher, Christian; Luehl, Anja; Falk, Florian C.; Lebedkin, Sergei; Kuehn, Michael; Wang, Cong; Paradies, Jan; Kappes, Manfred M.; Klopper, Wim; Roesky, Peter W. published the artcile< [2.2]Paracyclophanediyldiphosphane Complexes of Gold>, Electric Literature of 325168-88-5, the main research area is paracyclophanediyl diphosphine gold complex preparation crystal mol structure; alkyne hydroamination catalyst paracyclophanediyl diphosphine gold chloride complex; phosphorescence paracyclophanediyl diphosphine gold chloride complex.

Authors have prepared digold(I) complexes with the rigid-backbone diphosphine ligands PhanePhos, xyl-PhanePhos, and Ph2-GemPhos. All complexes were characterized by single-crystal x-ray diffraction, NMR, IR, Raman, and photoluminescence (PL) spectroscopy. [PhanePhos(AuCl)2] and [GemPhos(AuCl)2] show a very similar ligand scaffold, but different (aurophilic vs. nonaurophilic) intramol. Au-Au distances. Absorption and PL spectra of both compounds are quite similar. Theor. investigations reveal that the excited states are of different character (i.e., influenced by the Au-Au contacts). The resp. transition energies, however, lie close to each other, thus resulting in similar exptl. spectra. The gold atoms appear to produce a significant heavy-atom effect in the electronic relaxation dynamics. Thus, [PhanePhos(AuCl)2] and [GemPhos(AuCl)2] both show bright-green millisecond-long phosphorescence at low temperatures, although the latter is quenched at ambient temperature [PhanePhos(AuCl)2] and [GemPhos(AuCl)2] were also used as catalysts in the intra- and intermol. hydroamination of alkynes. Good to quant. conversions on a reasonable time scale were observed The overall performance of these catalysts in the studied reactions was similar, showing that Au-Au contacts do not have a major influence on the catalytic performance.

Cederbaum, Fredrik’s team published research in Advanced Synthesis & Catalysis in 2004-06-30 | 325168-88-5

Advanced Synthesis & Catalysis published new progress about Catalysts. 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Electric Literature of 325168-88-5.

Cederbaum, Fredrik; Lamberth, Clemens; Malan, Christophe; Naud, Fred; Spindler, Felix; Studer, Martin; Blaser, Hans-Ulrich published the artcile< Synthesis of substituted mandelic acid derivatives via enantioselective hydrogenation: Homogeneous versus heterogeneous catalysis>, Electric Literature of 325168-88-5, the main research area is stereoselective hydrogenation chlorophenylglyoxylate ruthenium homogeneous heterogeneous catalyst; chloromandelate stereoselective preparation ruthenium homogeneous heterogeneous catalyst; platinum cinchona catalyst stereoselective hydrogenation chlorophenylglyoxylate.

An extensive screening of both homogeneous and heterogeneous catalysts was carried out for the enantioselective hydrogenation of p-chlorophenylglyoxylic acid derivatives For p-chlorophenylglyoxylic amides only homogeneous Rh-diphosphine complexes gave satisfactory results, ees up to 87% were observed for the cy-oxo-pronop ligand. For Me p-chlorophenylglyoxylate both a homogeneous as well as a heterogeneous catalyst performed with ees >90%. A Pt catalyst modified with cinchona derivatives achieved 93% ee for the (R)- and 87% ee for the (S)-Me p-chloromandelate. A Ru-MeObiphep catalyst also reached 93% ee with TONs up to 4000 and TOFs up to 210 h-1. For all catalytic systems the effects of the metal, the nature of the chiral auxiliary and the solvent as well as of the reaction conditions were investigated. The homogeneous process was scaled up to the kg scale and the enantiomeric purity of the product was enhanced to >99% ee by two recrystallizations of the free p-chlorophenylmandelic acid.