October 11, 2022 | Page 2 of 3 | Chiral phosphine ligands

Wang, Duo-Sheng’s team published research in Chemical Science in 2011-04-30 | 139139-86-9

Chemical Science published new progress about Diastereoselective synthesis. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Computed Properties of 139139-86-9.

Wang, Duo-Sheng; Tang, Jie; Zhou, Yong-Gui; Chen, Mu-Wang; Yu, Chang-Bin; Duan, Ying; Jiang, Guo-Fang published the artcile< Dehydration triggered asymmetric hydrogenation of 3-(α-hydroxyalkyl)indoles>, Computed Properties of 139139-86-9, the main research area is stereoselective hydrogenation hydroxyalkyl indole reactant alkylindoline preparation; palladium catalyzed asym hydrogenation hydroxyalkyl indole reactant; hydroxyalkyl indole preparation formylation Grignard addition indole reactant.

Highly enantioselective hydrogenation of 3-(α-hydroxyalkyl)indoles promoted by a Bronsted acid for dehydration to form a vinylogous iminium intermediate in situ was developed with Pd(OCOCF3)2/(R)-H8-BINAP as catalyst with up to 97% ee. This methodol. provides an efficient and rapid access to chiral 2,3-disubstituted indolines, e.g. I (R1 = 5-F, 7-Me, R2 = H; R1 = H, R2 = 2-Me, 4-MeO, 4-F).

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

Rasson, Corentin’s team published research in Organic Process Research & Development in 2020-05-15 | 325168-88-5

Organic Process Research & Development published new progress about Allylation catalysts, stereoselective. 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Category: chiral-phosphine-ligands.

Rasson, Corentin; Riant, Olivier published the artcile< Copper(I) Diphosphine Bifluoride Complexes as Efficient Preactivated Catalysts for Nucleophilic Addition on Unsaturated Functional Groups>, Category: chiral-phosphine-ligands, the main research area is copper diphosphine bifluoride complex catalyst preparation nucleophilic addition; nucleophilic copper addition pronucleophile aldehyde ketone.

Herein we report the synthesis of a family of copper(I) diphosphine bifluoride complexes, their characterization, and their use as efficient preactivated catalysts for nucleophilic copper addition of pronucleophiles on unsaturations. Their use as mechanistic probes is also highlighted by the identification of two copper deuterides.

Roy, Amy H’s team published research in Journal of the American Chemical Society in 2003-07-23 | 277306-29-3

Journal of the American Chemical Society published new progress about Amination catalysts. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Related Products of 277306-29-3.

Roy, Amy H.; Hartwig, John F. published the artcile< Oxidative Addition of Aryl Tosylates to Palladium(0) and Coupling of Unactivated Aryl Tosylates at Room Temperature>, Related Products of 277306-29-3, the main research area is palladium oxidative addition phenyl tosylate mechanism kinetics; crystal structure palladium phenyl bromo ferrocene diphosphine chelate preparation; mol structure palladium phenyl bromo ferrocene diphosphine chelate; aryl tosylate unactivated cross coupling Grignard palladium catalyst; biaryl unsym preparation.

Aryl tosylates are attractive substrates for Pd-catalyzed cross-coupling reactions, but they are much less reactive than the more commonly used aryl triflates. The authors report the oxidative addition of aryl tosylates to Pd(PPF-t-Bu)[P(o-tolyl)3] [PPF-t-Bu = 1-diphenylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] and to Pd(CyPF-t-Bu)[P(o-tolyl)3] [CyPF-t-Bu = 1-dicyclohexylphosphino-2-(di-tert-butylphosphinoethyl)ferrocene] at room temperature to produce the corresponding Pd(II) aryl tosylate complexes (shown as I; R = Ph, X = OTs 3; R = cyclohexyl, X = OTs 4). In the presence of added bromide ions, arylpalladium(II) bromide complexes I (R = Ph, X = Br 5 ; R = cyclohexyl, X = Br 6) were formed. The structures of 5 and 6 were determined by x-ray crystallog. The rate of oxidative addition was accelerated by addition of either coordinating or weakly coordinating anions, and the reactions were faster in more polar solvents. The mild conditions for oxidative addition allowed the development of Pd-catalyzed Kumada couplings and amination reactions of unactivated aryl tosylates at room temperature The catalysts for these mild couplings of aryl tosylates were generated from Pd precursors and the sterically hindered Josiphos-type ligands that induced oxidative addition of aryl tosylates to Pd(0) at room temperature Thus, coupling reaction of XC6H4OTs (X = 2- and 4-MeO, 4-CF3, 4-Me) or of mesityl tosylate or of 1-naphthyl tosylate with aryl Grignard reagents ArMgBr (Ar = 4-tolyl, 4-FC6H4, 4-MeOC6H4) in PhMe in presence of 0.1-1.0 mol % Pd(dba)2 and PPF-t-Bu at either 25° or 80° gave the corresponding biaryls in 40-86% yields.

Trost, Barry M’s team published research in Journal of the American Chemical Society in 2008-09-10 | 152140-65-3

Journal of the American Chemical Society published new progress about Alkyl aryl ketones Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Synthetic Route of 152140-65-3.

Trost, Barry M.; Xu, Jiayi; Schmidt, Thomas published the artcile< Ligand Controlled Highly Regio- and Enantioselective Synthesis of α-Acyloxyketones by Palladium-Catalyzed Allylic Alkylation of 1,2-Enediol Carbonates>, Synthetic Route of 152140-65-3, the main research area is enediol carbonate allyl alkylation palladium catalysis ligand; acetoxyketone asym preparation.

The palladium-catalyzed decarboxylative asym. allylic alkylation of allyl 1,2-enediol carbonates can decompose to either α-hydroxyketones or α-hydroxyaldehydes. The product distribution is largely controlled by the ligand. Using Lnaph in DME the ketone product is obtained in good to excellent yields and high enantiomeric excesses. The reaction proceeds under extremely mild conditions and was tested with a broad range of ester substrates. Besides commonly used protection groups, such as OAc and OPiv, a more functionalized group, Me but-2-enoyl, is also used that can eventually afford other synthetically interesting structures.

Yen, Andy’s team published research in Organic Letters in 2019-09-20 | 277306-29-3

Organic Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent) (Oxabicyclic). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene.

Yen, Andy; Pham, Anh Hoang; Larin, Egor M.; Lautens, Mark published the artcile< Rhodium-Catalyzed Enantioselective Synthesis of Oxazinones via an Asymmetric Ring Opening-Lactonization Cascade of Oxabicyclic Alkenes>, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is oxabicyclic alkene amino acid ester rhodium ring opening lactonization; oxazinone stereoselective preparation.

The rhodium-catalyzed asym. ring opening reaction of oxabicyclic alkenes is shown to be an efficient method for synthesizing chiral heterocycles. We demonstrate that the pairwise combination of chiral catalyst with chiral amino-acid-derived pronucleophiles results in a stereodivergent synthesis of diastereomeric hydroxyesters. A favorable conformational preference induces the subsequent lactonization of one diastereomer leading to the highly enantioselective synthesis of oxazinones.

Jiang, Quanbin’s team published research in Advanced Synthesis & Catalysis in 2013 | 139139-93-8

Advanced Synthesis & Catalysis published new progress about Alkyl aryl ketones Role: SPN (Synthetic Preparation), PREP (Preparation) (β-aryl). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Electric Literature of 139139-93-8.

Jiang, Quanbin; Guo, Tenglong; Wang, Qingfu; Wu, Ping; Yu, Zhengkun published the artcile< Rhodium(I)-Catalyzed Arylation of β-Chloro Ketones and Related Derivatives through Domino Dehydrochlorination/ Conjugate Addition>, Electric Literature of 139139-93-8, the main research area is chloro ketone rhodium arylation dehydrochlorination conjugate addition catalyst; aryl ketone preparation.

Highly efficient arylations of β-chloro ketones and their ester and amide derivatives were achieved by means of domino dehydrochlorination/Rh(I)-catalyzed conjugate addition In situ generated vinyl ketones and their analogs were identified as the reaction intermediates. The present synthetic protocol provides a concise route to (chiral) β-aryl ketones, esters, and amides.

Chen, Yi’s team published research in Organic Letters in 2021-01-01 | 152140-65-3

Organic Letters published new progress about Alkaloids Role: SPN (Synthetic Preparation), PREP (Preparation) (akuammiline core structure). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, HPLC of Formula: 152140-65-3.

Chen, Yi; Song, Xuanyi; Gao, Lu; Song, Zhenlei published the artcile< Intramolecular Sakurai Allylation of Geminal Bis(silyl) Enamide with Indolenine. A Diastereoselective Cyclization To Form Functionalized Hexahydropyrido[3,4-b]Indole>, HPLC of Formula: 152140-65-3, the main research area is Sakurai allylation enamide indolenine diastereoselective cyclization; hexahydropyridoindole diastereoselective synthesis; akuammiline alkaloid core synthesis Sakurai allylation fluoride.

A fluoride-promoted intramol. Sakurai allylation of geminal bis(silyl) enamide with indolenine has been developed. The reaction facilitates an efficient cyclization to give hexahydropyrido[3,4-b]indoles in good yields with high diastereoselectivity. The resulted cis,trans-stereochem. further enables the ring-closing metathesis (RCM) reaction of two alkene moieties, giving a tetracyclic N-heterocycle I widely found as the core structure in akuammiline alkaloids.

Zhang, Ze-Xin’s team published research in Angewandte Chemie, International Edition in 2016 | 152140-65-3

Angewandte Chemie, International Edition published new progress about Cyclization, stereoselective. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Synthetic Route of 152140-65-3.

Zhang, Ze-Xin; Chen, Si-Cong; Jiao, Lei published the artcile< Total Synthesis of (+)-Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization>, Synthetic Route of 152140-65-3, the main research area is minfiensine synthesis asym cascade cyclization; monoterpene indole alkaloid core structure preparation asym cascade cyclization; alkaloids; cyclizations; natural products; palladium; total synthesis.

A new method for one-step construction of the tetracyclic core structure of the indole alkaloid (+)-minfiensine was developed utilizing a palladium-catalyzed asym. indole dearomatization/iminium cyclization cascade. An efficient total synthesis of (+)-minfiensine was realized using this strategy. The present method enables access to the common core structure of a series of monoterpene indole alkaloids, such as vincorine, echitamine, and aspidosphylline A.

Lipshutz, Bruce H’s team published research in Synthesis in 2007-10-16 | 277306-29-3

Synthesis published new progress about Esters, α,β-unsaturated Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Application In Synthesis of 277306-29-3.

Lipshutz, Bruce H.; Lee, Ching-Tien; Taft, Benjamin R. published the artcile< A conjugate reduction pathway to chiral silanes using CuH>, Application In Synthesis of 277306-29-3, the main research area is ester carboxylic silylated chiral preparation asym reduction hydrosilylation enoate; copper hydride ferrocenylphosphine catalyst asym reduction hydrosilylation enoate; silane carboxyalkyl chiral preparation asym reduction silyl enoate.

Asym. reduction of β-silyl α,β-unsaturated esters was achieved by CuH/(R,S)-PPF-P(tBu)2 reagent, affording chiral β-silylated arylalkanoate esters. β-Silyl enoates (Z)- and (E)-PhMe2SiCR:CHCO2R1 [(Z)-2, (E)-2, resp.] were prepared by Peterson or Horner-Wadsworth-Emmons olefination, resp., of the corresponding acylsilanes PhMe2SiCOR. The compounds 2 were reduced by CuH-catalyzed conjugate hydrosilylation by polymethylhydrosiloxane in the presence of chiral ferrocenylphosphine, (R,S)-1-[1-(di-tert-butylphosphino)ethyl]-2-diphenylphosphinoferrocene (1). Exptl. details concerning asym. 1,4-reduction of β-silylated-β,β-disubstituted enoates catalyzed by CuH are described.

Driver, Tom G’s team published research in Journal of the American Chemical Society in 2007-04-04 | 325168-88-5

Journal of the American Chemical Society published new progress about Hydroperoxides Role: PUR (Purification or Recovery), RCT (Reactant), SPN (Synthetic Preparation), PREP (Preparation), RACT (Reactant or Reagent). 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Formula: C48H50P2.

Driver, Tom G.; Harris, Jason R.; Woerpel, K. A. published the artcile< Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines: Preparation of Enantioenriched Tertiary Hydroperoxides>, Formula: C48H50P2, the main research area is hydroperoxide tertiary reductive kinetic resolution cyclophane phosphine.

An efficient reductive kinetic resolution strategy capable of accessing optically active tertiary hydroperoxides R1R2C(Ph)OOH (R1 = H, Me; R2 = Et, n-Pr, Me2CH, cyclohexyl, Me3CSiMe2OCH2, etc.) is reported. Readily accessible tertiary hydroperoxides are resolved with com. available (R)- or (S)-xylyl-PHANEPHOS with selectivity factors as large as 37. The resulting bis(phosphine oxide) can be recycled in high yields. The isolated mono(phosphine oxide) intermediate resolved hydroperoxides with the same selectivity as the parent bis-phosphine.