October 2022 | Page 39 of 44 | Chiral phosphine ligands

Nishida, Goushi’s team published research in Angewandte Chemie, International Edition in 2008 | 139139-86-9

Angewandte Chemie, International Edition published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent) (1,6-diynes). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Category: chiral-phosphine-ligands.

Nishida, Goushi; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken published the artcile< Enantioselective synthesis of P-stereogenic alkynylphosphine oxides by Rh-catalyzed [2+2+2] cycloaddition>, Category: chiral-phosphine-ligands, the main research area is alkynyl phosphine oxide preparation stereoselective structure; cycloaddition dialkynyl phosphine oxide diyne rhodium binap complex catalyst; crystal mol structure stereogenic phosphorus alkynyl phosphine oxide preparation.

An enantioselective synthesis of P-stereogenic alkynylphosphine oxides through a cationic rhodium(l)/modified-binap complex catalyzed [2+2+2] cycloaddition of sym. dialkynylphosphine oxides with 1,6-diynes was developed (binap = 2,2′-bis(diphenylphosphinyl)-1,1′-binaphthyl, Z = CH2, O, or N-sulfonamide). Furthermore, this method permits the synthesis of a C2-sym. P-stereogenic bis(alkynylphosphine oxide). A crystal structure of one product was determined along with the absolute configuration of the phosphorus center.

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

Fernandez, Marti’s team published research in Advanced Synthesis & Catalysis in 2016 | 139139-86-9

Advanced Synthesis & Catalysis published new progress about Alkadiynes Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, COA of Formula: C44H40P2.

Fernandez, Marti; Parera, Magda; Parella, Teodor; Lledo, Agusti; Le Bras, Jean; Muzart, Jacques; Pla-Quintana, Anna; Roglans, Anna published the artcile< Rhodium-Catalyzed [2+2+2] Cycloadditions of Diynes with Morita-Baylis-Hillman Adducts: A Stereoselective Entry to Densely Functionalized Cyclohexadiene Scaffolds>, COA of Formula: C44H40P2, the main research area is cyclohexadiene scaffold enantioselective preparation; diyne Morita Baylis Hillman adduct enantioselective cycloaddition rhodium catalyst.

A rhodium-catalyzed asym. synthesis of 5,5-disubstituted cyclohexa-1,3-dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita-Baylis-Hillman (M-B-H) adducts as unsaturated substrates. Products containing two adjacent chiral centers (quaternary and tertiary, resp.) were obtained with complete diastereoselectivity and high enantioselectivity (84-97%) through a kinetic resolution of the M-B-H adduct. Furthermore, these highly substituted cyclohexadienes reacted with dienophiles to afford the corresponding Diels-Alder cycloadducts in good yields.

Trost, Barry M’s team published research in Journal of the American Chemical Society in 2008-10-29 | 152140-65-3

Journal of the American Chemical Society 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].

Trost, Barry M.; Thaisrivongs, David A. published the artcile< Strategy for Employing Unstabilized Nucleophiles in Palladium-Catalyzed Asymmetric Allylic Alkylations>, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is strategy employing unstabilized nucleophile palladium catalyzed asym allylic alkylation.

The authors report a strategy for the employment of highly unstabilized anions in palladium-catalyzed asym. allylic alkylations (AAA). The hard 2-methylpyridyl nucleophiles studied are first reacted in situ with BF3•OEt2; subsequent deprotonation of the resulting complexes with LiHMDS affords soft anions that are competent nucleophiles in AAA reactions. The reaction is selective for the 2-position of methylpyridines and tolerates bulky aryl and alkyl substitution at the 3-, 4-, and 5-positions. Studies into the reaction mechanism demonstrate that the configuration of the allylic stereocenter is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed allylic substitution processes of stabilized anions.

Bates, Roderick W’s team published research in Asian Journal of Organic Chemistry in 2014 | 152140-65-3

Asian Journal of Organic Chemistry published new progress about Cross-metathesis. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Application In Synthesis of 152140-65-3.

Bates, Roderick W.; Li, Lu; Palani, Kalpana; Phetsang, Wanida; Loh, Joanna Kejun published the artcile< Synthesis of the Tetrahydropyran Fragment of Bistramide D>, Application In Synthesis of 152140-65-3, the main research area is bistramide D tetrahydropyran fragment enantioselective preparation.

A synthesis of the tetrahydropyran (THP) moiety of bistramide D has been completed by using cross-metathesis and kinetically controlled intramol. oxa-Michael addition to form the ring with excellent trans selectivity. The C9 Me substituent was introduced by using an unsaturated sulfone building block, which can be most effectively prepared through a combination of diastereoselective allylation and alkene isomerisation. The effect of this Me group on subsequent cross-metathesis reactions can be mitigated by careful choice of reaction conditions.

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).

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.