October 2022 | Page 26 of 44 | Chiral phosphine ligands

Williams, David R’s team published research in Journal of the American Chemical Society in 2014-06-18 | 139139-93-8

Journal of the American Chemical Society published new progress about Cyclization (Pauson-Khand [2+2+1]-carbocyclization). 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.

Williams, David R.; Shah, Akshay A. published the artcile< Total Synthesis of (+)-Ileabethoxazole via an Iron-Mediated Pauson-Khand [2 + 2 + 1] Carbocyclization>, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is ileabethoxazole total synthesis Pauson Khand carbocyclization iron; Stille cross coupling total synthesis ileabethoxazole; insertion total synthesis ileabethoxazole; asym hydride reduction copper total synthesis ileabethoxazole.

Studies describe the total synthesis of (+)-ileabethoxazole (I) using a Stille cross-coupling reaction of propargylic stannanes with 5-iodo-1,3-oxazoles to produce 1,1-disubstituted allenes. An iron-mediated [2+2+1] carbocyclization yields a novel cyclopentenone II (R = H, Me) for elaboration to I. Site-selective palladium insertion reactions allow for regiocontrolled substitutions of the heterocycle. Asym. copper hydride reductions are examined, and strategies for the formation of the central aromatic ring are discussed.

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

Bandini, Marco’s team published research in Journal of Organometallic Chemistry in 2010 | 325168-88-5

Journal of Organometallic Chemistry published new progress about Allylic alcohols Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Reference of 325168-88-5.

Bandini, Marco; Gualandi, Andrea; Monari, Magda; Romaniello, Alessandro; Savoia, Diego; Tragni, Michele published the artcile< Allylic alcohols: Valuable synthetic equivalents of non-activated alkenes in gold-catalyzed enantioselective alkylation of indoles>, Reference of 325168-88-5, the main research area is allylic alc tethered indole derivative preparation; chiral ligand gold catalyzed intramol allylic alkylation indole derivative; tetrahydrocarbazole derivative stereoselective preparation; tetrahydrocarboline derivative stereoselective preparation.

The recent booming of gold catalysis has demonstrated that unprecedented transformations can be realized in a highly selective manner. Moreover, due to the growing availability of chiral organic ligands, gold-catalysis can be considered as one of most dynamic hot spots in asym. synthesis. However, in this context, the use of non-activated olefinic C-C double bonds is still largely unexplored due to the intrinsic inertness of C=C (respect to allenes and alkynes) in taking part in nucleophilic additions assisted by π-electrophilic activations. Allylic alcs. have been demonstrated to be feasible “”surrogates”” of non-activated alkenes for the enantioselective allylic alkylation of indoles catalyzed by chiral gold(I) complexes. In this investigation, a full account addressing efficiency and substrate scope of such a process is presented. The products, tetrahydrocarbazoles or tetrahydro-β-carbolines, are obtained in moderate to good yields and 40-86% ee from the corresponding Z-allylic alc.-containing substrates, while the E isomers are unreactive.

Tanaka, Ken’s team published research in Journal of the American Chemical Society in 2007-02-14 | 139139-86-9

Journal of the American Chemical Society published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Safety of (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Tanaka, Ken; Sagae, Hiromi; Toyoda, Kazuki; Noguchi, Keiichi; Hirano, Masao published the artcile< Enantioselective Synthesis of Planar-Chiral Metacyclophanes through Rhodium-Catalyzed Alkyne Cyclotrimerization>, Safety of (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is metacyclophane asym synthesis; alkyne stereoselective cyclotrimerization rhodium catalyst.

The first catalytic enantioselective synthesis of planar-chiral metacyclophanes via cationic rhodium(I)/(R)-H8-BINAP complex-catalyzed alkyne cyclotrimerization is described. This reaction represents a versatile new method for the preparation of planar-chiral [7]-[10]metacyclophanes.

Trost, Barry M’s team published research in Journal of the American Chemical Society in 2009-05-13 | 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, Related Products 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. [Erratum to document cited in CA149:307451]>, Related Products of 152140-65-3, the main research area is erratum enediol carbonate allyl alkylation palladium catalysis ligand; acetoxyketone asym preparation erratum.

On page 11853, in Table 2, entries 11 and 12, the stereochem. assignments of the cyclohexenyl ring of compound 20 and the cycloheptenyl ring of compound 22 should be S, not R. This assignment is based on the empirical model we proposed (Trost,B.M.; Toste, F.D. J. Am. Chem.Soc. 1999, 121,4545), which has been supported by extensive exptl. data.

Zhou, Huan’s team published research in Angewandte Chemie, International Edition in 2017 | CAS: 210169-54-3

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: rhodium-catalyzed asymmetric formal olefination or cycloaddition of 1,3-dicarbonyl compounds with 1,6-diynes or 1,6-enynes, stereoselective preparation of homoallylic alcohols via Ir-catalyzed stereoselective transfer hydrogenative crotylation of an allylic acetate with alcohols or aldehydesApplication of 210169-54-3

In 2017,Zhou, Huan; Liu, Yuan; Yang, Suhua; Zhou, Le; Chang, Mingxin published 《One-Pot N-Deprotection and Catalytic Intramolecular Asymmetric Reductive Amination for the Synthesis of Tetrahydroisoquinolines》.Angewandte Chemie, International Edition published the findings.Application of 210169-54-3 The information in the text is summarized as follows:

A one-pot N-Boc deprotection and catalytic intramol. reductive amination protocol for the preparation of enantiomerically pure tetrahydroisoquinoline alkaloids is described. The iodine-bridged dimeric iridium complexes displayed superb stereoselectivity to give tetrahydroisoquinolines, including several key pharmaceutical drug intermediates, in excellent yields under mild reaction conditions. Three additives played important roles in this reaction: titanium(IV) isopropoxide and mol. iodine accelerated the transformation of the intermediate imine to the tetrahydroisoquinoline product; p-toluenesulfonic acid contributed to the stereocontrol.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Application of 210169-54-3) was used in this study.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Gupta, Naveen’s team published research in European Journal of Organic Chemistry in 2018 | CAS: 210169-54-3

In 2018,Gupta, Naveen; Tak, Rajkumar; Nazish, Mohd; Jakhar, Ajay; Khan, Noor-ul H.; Kureshy, Rukhsana I. published 《Copper(II) Triflate Catalyzed Regioselective and Enantioselective Propargylation of Isatin Derivatives by Using Allenylboronic Acid Pinacol Ester》.European Journal of Organic Chemistry published the findings.COA of Formula: C38H28O4P2 The information in the text is summarized as follows:

The authors report a simple protocol for the synthesis of homopropargyl alcs. with isatin derivatives under milder conditions for the first time. The excellent regioselectivity and yields were observed with copper triflate as a Lewis-acid catalyst and allenylboronic acid pinacol ester as a nucleophile in aqueous media. A gram-scale synthesis was done to check the efficiency of the protocol with retention in selectivity. Further one-step functionalization of these homopropargyl alcs. was established as the synthetic application of these alkynes. The enantioselective synthesis of these chiral propargyl alcs. also was explored for the first time with an enantiomeric ratio up to 12:88. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3COA of Formula: C38H28O4P2)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Pongracz, Peter’s team published research in Journal of Organometallic Chemistry in 2017 | CAS: 210169-54-3

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: regio- and stereoselective preparation of axially chiral arylnaphthalene derivatives via rhodium-catalyzed [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives or diastereo- and enantioselective hydrogenation of α-amino-β-keto ester hydrochlorides catalyzed by an iridium complex.Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2017 ,《Rhodium-catalyzed hydroformylation in γ-valerolactone as a biomass-derived solvent》 was published in Journal of Organometallic Chemistry. The article was written by Pongracz, Peter; Bartal, Brigitta; Kollar, Laszlo; Mika, Laszlo T.. The article contains the following contents:

Rhodium-catalyzed hydroformylation of styrene, α-methylstyrene, di-Me itaconate, and (R)-limonene was performed in gamma-valerolactone (GVL) as a proposed biomass-based environmentally benign solvent for hydroformylation referring to toluene as a generally used conventional solvent. Both achiral (triphenylphosphine, 1,3-bis(diphenylphoshino)propane) and enantiopure bidentate phosphine ligands ((S,S)-BDPP, (R)-BINAP, (R)-QUINAP, (R,R)-DIOP, (Rc),(Sp)-JOSIPHOS, (S)-SEGPHOS, (S)-(DM)-SEGPHOS) were investigated in in situ generated Rh-diphosphine catalyst systems. In general, the catalysts’ activity in GVL was lower than in toluene; however, remarkable chemo- (>99%) and regioselectivities (>95%) were achieved in GVL under identical conditions. The BDPP-modified Rh-catalyst was recycled for three consecutive cycles; however a decrease in its activity was detected. In the experiment, the researchers used many compounds, for example, (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Quality Control of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Li, Zhanyu’s team published research in Journal of the American Chemical Society in 2017 | CAS: 256390-47-3

(R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. These intermediates are formed through nucleophilic attack of the phosphine catalysts at electron-poor nuclei (normally carbon atoms) and then proceed through several steps to form new chemical bonds. Category: chiral-phosphine-ligands

《Asymmetric Nitrone Synthesis via Ligand-Enabled Copper-Catalyzed Cope-Type Hydroamination of Cyclopropene with Oxime》 was written by Li, Zhanyu; Zhao, Jinbo; Sun, Baozhen; Zhou, Tingting; Liu, Mingzhu; Liu, Shuang; Zhang, Mengru; Zhang, Qian. Category: chiral-phosphine-ligands And the article was included in Journal of the American Chemical Society on August 30 ,2017. The article conveys some information:

We report realization of the first enantioselective Cope-type hydroamination of oximes for asym. nitrone synthesis. The ligand promoted asym. cyclopropene “”hydronitronylation”” process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C-N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis. After reading the article, we found that the author used (R)-(6,6′-Dimethoxybiphenyl-2,2′-diyl)bis[bis(3,4,5-trimethoxyphenyl)phosphine](cas: 256390-47-3Category: chiral-phosphine-ligands)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Haydl, Alexander M.’s team published research in Chemistry – A European Journal in 2016 | CAS: 1221746-56-0

(R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene(cas: 1221746-56-0) belongs to chiral phosphine ligands. Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates. These intermediates are formed through nucleophilic attack of the phosphine catalysts at electron-poor nuclei (normally carbon atoms) and then proceed through several steps to form new chemical bonds. Quality Control of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene

The author of 《Regioconvergent and Enantioselective Rhodium-Catalyzed Hydroamination of Internal and Terminal Alkynes: A Highly Flexible Access to Chiral Pyrazoles》 were Haydl, Alexander M.; Hilpert, Lukas J.; Breit, Bernhard. And the article was published in Chemistry – A European Journal in 2016. Quality Control of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene The author mentioned the following in the article:

In the presence of (cyclooctadiene)rhodium(I) chloride dimer, a nonracemic ferrocenyldiphosphine monoxide, and pyridine p-toluenesulfonate (PPTS), 1-aryl-1-propynes such as RCCMe (R = Ph, 4-MeC6H4, 4-F3CC6H4, 4-PhC6H4, 2-naphthyl, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-MeCOC6H4, 4-O2NC6H4, PinB; PinB = 4,4,5,5-tetramethyl-1,3-dioxo-2-borolan-2-yl), phenylallene, and selected 1-aryl-2-propynes underwent chemoselective, regioselective, and enantioselective addition reactions with 1H-pyrazoles to yield nonracemic N1-allylic pyrazoles such as I (R = Ph, 4-MeC6H4, 4-F3CC6H4, 4-PhC6H4, 2-naphthyl, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-MeCOC6H4, 4-O2NC6H4, PinB) in 65-97% yields, in 68:32->99:1 regioselectivities, and in 80:20-97.5:2.5 er (or, for nonracemic pyrazoles, 82:18 or 85:15 dr). The method tolerated a variety of functional groups in the alkyne and pyrazole components. The structure of a phenylallylated stanozolol was determined by X-ray crystallog. In the experimental materials used by the author, we found (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene(cas: 1221746-56-0Quality Control of (R)-1-[(R)-1-(Di-tert-butylphosphino)ethyl]-2-[(R)-phenylphosphinoyl]ferrocene)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Lou, Yazhou’s team published research in Angewandte Chemie, International Edition in 2018 | CAS: 210169-54-3

In 2018,Lou, Yazhou; Hu, Yutao; Lu, Jiaxiang; Guan, Fanfu; Gong, Gelin; Yin, Qin; Zhang, Xumu published 《Dynamic Kinetic Asymmetric Reductive Amination: Synthesis of Chiral Primary β-Amino Lactams》.Angewandte Chemie, International Edition published the findings.Computed Properties of C38H28O4P2 The information in the text is summarized as follows:

A highly efficient ruthenium-catalyzed asym. reductive amination (ARA) of racemic β-keto lactams with mol. hydrogen and ammonium salts is disclosed for the synthesis of enantiomerically pure primary amino lactams through dynamic kinetic resolution (DKR). By this approach, a range of syn primary β-amino lactams I (R= Me, Et, iso-Pr etc. n= 1, 2) were obtained in high yields with high chemo-, enantio-, and diastereoselectivity (up to 98 % yield, 99 % ee, >20:1 d.r., syn products). The utility of the products has been demonstrated by rapid access to a key synthetic intermediate towards biol. active drug mols. Meanwhile, mechanistic studies and control experiments indicate that the reaction may proceed through the hydrogenation of an iminium intermediate. In the experiment, the researchers used (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Computed Properties of C38H28O4P2)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis