Day: February 23, 2023

Palladium-Catalyzed Enantioselective Arylation of Racemic Ketones to Form Bridged Bicycles via Dynamic Kinetic Resolution was written by Huang, Xiaolei;Oh, William Ray Jun Jie;Zhou, Jianrong Steve. And the article was included in Angewandte Chemie, International Edition in 2018.Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine This article mentions the following:

Enantioselective α-arylation of racemic ketones containing existing α’-stereocenters is reported for the first time via base-induced dynamic kinetic resolution Bridged bicyclic rings are formed in good ee values, which are difficult to obtain otherwise. Furthermore, reactions in DMSO-d₆ resulted in extensive deuteration of both α- and α’-positions in the products, thus supporting a pathway involving rapid, reversible deprotonation of ketones under catalytic conditions. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Name: (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Regioselective hydroesterification of styrene catalyzed by cationic palladium(II) complexes under mild conditions was written by Oi, S.;Nomura, M.;Aiko, T.;Inoue, Y.. And the article was included in Journal of Molecular Catalysis A: Chemical in 1997.Electric Literature of C33H25OP This article mentions the following:

The cationic palladium(II) complex [Pd(MeCN)₂(PPh₃)₂](BF₄)₂ was found to be an active catalyst for hydroesterification (alkoxycarbonylation) of styrene using CO and methanol under very mild conditions. The system, Pd(OAc)₂-PPh₃–p-toluenesulfonic acid, which should give rise to a cationic species in situ, was also effective to produce the branched ester regioselectively in an excellent yield at ambient temperature Asym. hydroesterification of styrene by the use of chiral phosphines as ligands was also studied. The hydroesterification of 4-isobutylstyrene gave α-methyl-4-(2-methylpropyl)benzeneacetic acid Me ester (i.e., ibuprofen Me ester). Also prepared was (S)-6-methoxy-α-methyl-2-naphthaleneacetic acid Me ester. In the experiment, the researchers used many compounds, for example, (S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9Electric Literature of C33H25OP).

(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphine (cas: 134484-36-9) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Indeed, very little research on chiral tertiary phosphine-catalyzed asymmetric reactions occurred prior to the year 2000.Electric Literature of C33H25OP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric allylation of aryl aldehydes: studies on the scope and mechanism of the palladium catalyzed diethylzinc mediated umpolung using phosphoramidite ligands was written by Howell, Gareth P.;Minnaard, Adriaan J.;Feringa, Ben L.. And the article was included in Organic & Biomolecular Chemistry in 2006.Product Details of 185449-81-4 This article mentions the following:

Using modular, monodentate phosphoramidite ligands, enantioselective palladium catalyzed diethylzinc mediated allylation of aldehydes was achieved. The scope of the asym. C-C bond formation was investigated with respect to nucleophilic and electrophilic components and an alternative reaction mechanism is proposed based on our findings. In the experiment, the researchers used many compounds, for example, (S)-4-(Dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)morpholine (cas: 185449-81-4Product Details of 185449-81-4).

(S)-4-(Dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yl)morpholine (cas: 185449-81-4) belongs to chiral phosphine ligands. Thousands of arylphosphines have been used as chiral ligands for metal-catalyzed asymmetric reactions. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.Product Details of 185449-81-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Synthesis of novel chiral phosphine-olefin complexes and their evaluation as ligands in the rhodium-catalyzed asymmetric 1,4-addition was written by Stemmler, Rene T.;Bolm, Carsten. And the article was included in Synlett in 2007.COA of Formula: C26H28FeNP This article mentions the following:

Novel chiral phosphine-olefin complexes containing ferrocene and cyrhetrene backbones were synthesized and evaluated as ligands in the Rh-catalyzed 1,4-addition of phenylboronic acid to cyclohexenone. The highest efficiency in this series was observed with planar-chiral ligands (S_p)-1-(diphenylphosphino)-2-vinylferrocene and (S_p)-tricarbonyl[η⁵-1-(diphenylphosphino)-2-ethenylcyclopentadienyl]rhenium, which furnished the corresponding product with up to 71% ee. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2COA of Formula: C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.COA of Formula: C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Palladium-catalyzed DYKAT of butadiene mono-epoxide: enantioselective total synthesis of (+)-DMDP, (-)-bulgecinine, and (+)-broussonetine G was written by Trost, Barry M.;Horne, Daniel B.;Woltering, Michael J.. And the article was included in Chemistry – A European Journal in 2006.SDS of cas: 174810-09-4 This article mentions the following:

Palladium catalyzed DYKAT (dynamic kinetic asym. transformation) allylic alkylation reaction of an amine with two equivalent of butadiene monoxide allows for the expedient synthesis of trans- and cis-2,5-dihydropyrroles. The versatility of these chiral synthons towards the synthesis of a wide variety of imino-sugar natural products was demonstrated with the short and high yielding asym. syntheses of (+)-DMDP, and (-)-bulgecinine. In addition, the first total synthesis of (+)-broussonetine G, a potent glycosidase inhibitor, is described along with the assignment of its relative and absolute stereochem. configuration. In the experiment, the researchers used many compounds, for example, N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4SDS of cas: 174810-09-4).

N,N’-((1R,2R)-Cyclohexane-1,2-diyl)bis(2-(diphenylphosphino)-1-naphthamide) (cas: 174810-09-4) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Over the last decade, however, and especially since 2005, considerable progress has been made in asymmetric phosphine catalysis.SDS of cas: 174810-09-4

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Chiral paramagnetic closo-ruthenacarboranes via phosphine-diphosphine displacement reaction of “three-bridge” exo-nido-ruthenacarboranes: Molecular Structure of (-)-[closo-3-Cl-3,3-{(Ph₂PCHCH₃)₂CH₂}-3,1,2-RuC₂B₉H₁₁] and its ortho-cycloboronated derivative was written by Cheredilin, Dmitri N.;Kadyrov, Renat;Dolgushin, Fedor M.;Balagurova, Elena V.;Godovikov, Ivan A.;Solodovnikov, Stanislav P.;Chizhevsky, Igor T.. And the article was included in Inorganic Chemistry Communications in 2005.SDS of cas: 77876-39-2 This article mentions the following:

Ruthenacarboranes with chiral non-racemic (2S,4S)-2,4-bis(diphenylphosphino)pentane ligand were prepared by ligand substitution and cage closing of ruthenium nido-carborane complexes. Treatment of [exo-nido-[Cl(Ph₃P)₂Ru]-(μ-H)₃-10-H-7,8-C₂B₉H₈] (1) with the (2S,4S)-(-)-2,4-bis(diphenylphosphino)pentane (3, BDPP) in toluene results in the formation of three novel optically active diphosphine-ruthenium closo complexes, 18e diamagnetic (-)-[closo-3-Cl-3,3-[(S,S)-BDPP]-3-H-3,1,2-RuC₂B₉H₁₁] (4), and 17e paramagnetic (-)-[closo-3-Cl-3,3-[(S,S)-BDPP]-3,1,2-RuC₂B₉H₁₁] (5) along with its ortho-cycloboronated derivative (-)-[closo-3-Cl-3,3-[(S,S)-Ph₂PCH(CH₃)CH₂CH(CH₃)PPh-ortho-C₆H₄]-3,1,2-RuC₂B₉H₁₀] (6). Both odd-electron complexes 5 and 6 were characterized by single-crystal x-ray diffraction anal. In the experiment, the researchers used many compounds, for example, (2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2SDS of cas: 77876-39-2).

(2S,4S)-Pentane-2,4-diylbis(diphenylphosphine) (cas: 77876-39-2) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Indeed, very little research on chiral tertiary phosphine-catalyzed asymmetric reactions occurred prior to the year 2000.SDS of cas: 77876-39-2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric synthesis catalyzed by chiral ferrocenylphosphine-transition metal complexes. I. Preparation of chiral ferrocenylphosphines was written by Hayashi, Tamio;Mise, Takaya;Fukushima, Motoo;Kagotani, Masahiro;Nagashima, Nobuo;Hamada, Yuji;Matsumoto, Akira;Kawakami, Sota;Konishi, Mitsuo. And the article was included in Bulletin of the Chemical Society of Japan in 1980.Computed Properties of C26H28FeNP This article mentions the following:

As chiral ligands for transition metal complex catalyzed asym. reactions, various kinds of chiral ferrocenylphosphines, which have planar chirality due to 1,2-unsym. substituted ferrocene structure and also have a functional group on the side chain of the ferrocene nucleus, were prepared (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine, (S)-N,N-dimethyl-1-[(R)-1′,2-bis(diphenylphosphino)ferrocenyl]ethylamine and their dimethylphosphino derivatives were prepared by lithiation of optically resolved N,N-dimethyl-1-ferrocenylethylamine. The 1-(dimethylamino)ethyl group on the ferrocenylphosphines was converted stereospecifically by nucleophilic substitution reactions into 1-methoxy-, 1-hydroxy-, 1-diphenylphosphino-, and several 1-(dialkylamino)ethyl groups. 1-(Diphenylphosphino)-2-(dimethylaminomethyl)ferrocene was optically resolved via its phosphine sulfide dibenzoyltartaric acid salt. The relationship between CD spectra of the chiral ferrocenylphosphines and the configuration of their chirality is discussed. In the experiment, the researchers used many compounds, for example, (R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2Computed Properties of C26H28FeNP).

(R)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (cas: 55700-44-2) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Trivalent phosphorus compounds called phosphines have a tetrahedral electron-group geometry which makes them structurally analogous to amines.Computed Properties of C26H28FeNP

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric Hydrogenation of α-Purine Nucleobase-Substituted Acrylates with Rhodium Diphosphine Complexes: Access to Tenofovir Analogues was written by Sun, Huan-Li;Chen, Fei;Xie, Ming-Sheng;Guo, Hai-Ming;Qu, Gui-Rong;He, Yan-Mei;Fan, Qing-Hua. And the article was included in Organic Letters in 2016.Application In Synthesis of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) This article mentions the following:

The first asym. hydrogenation of α-purine nucleobase-substituted α,β-unsaturated esters, catalyzed by a chiral rhodium (R)-Synphos catalyst, has been developed. A wide range of mono- and disubstituted acrylates were successfully hydrogenated under very mild conditions in high yields with good to excellent enantioselectivities (up to 99% ee). This method provides a convenient approach to the synthesis of a new kind of optically pure acyclic nucleoside and Tenofovir analogs. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1Application In Synthesis of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine)).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Application In Synthesis of (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Supercritical fluid chromatography comparison of the poly(trans-1,2-cyclohexanediyl-bis acrylamide) (P-CAP) column with several derivatized polysaccharide-based stationary phases was written by Barnhart, Wesley W.;Gahm, Kyung H.;Hua, Zheng;Goetzinger, Wolfgang. And the article was included in Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences in 2008.SDS of cas: 37002-48-5 This article mentions the following:

The poly(trans-1,2-cyclohexanediyl-bisacrylamide) (P-CAP) column has so far been primarily used with normal phase and polar organic mobile phase chromatog. Its use in supercritical fluid chromatog. (SFC) was studied via the anal. of 40 com. and 100 proprietary compounds using a 12-min gradient with methanol as a modifier. Results were then compared against those obtained from the popular derivatized polysaccharide-based chiral stationary phases (CSPs) such as Chiralpak AD-H and Chiralpak AS-H as well as Chiralcel OD-H and Chiralcel OJ-H columns. P-CAP demonstrated separation of 25% of the 140 total compounds, while each of the derivatized polysaccharide-based CSPs separated at least 46%. A study that compared the loading of 1,1′-bi-2-naphthol with P-CAP and Chiralpak AS columns indicated a similar trend in resolution vs. amount injected, though AS appeared capable of allowing a greater loading of material. The P-CAP column is beneficial in the separation of a complex mixture of enantiomers and achiral impurities, where the derivatized polysaccharide-based columns did not show as desirable of a separation A key advantage of this type of chiral stationary phase is the fact that it is available in both enantiomeric forms, allowing manipulation of elution order of enantiomers, which is especially helpful for preparative applications. P-CAP also demonstrated that it could resolve an achiral impurity from the desired compound in a different mixture, while the same impurity coeluted on the Chiralpak AD-H column. Overall, the synthetic polymer-based P-CAP showed less chiral discrimination power compared to the derivatized polysaccharide-based CSPs under the conditions explored. In the experiment, the researchers used many compounds, for example, (((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5SDS of cas: 37002-48-5).

(((4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene))bis(diphenylphosphine) (cas: 37002-48-5) belongs to chiral phosphine ligands. Thousands of arylphosphines have been used as chiral ligands for metal-catalyzed asymmetric reactions. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. SDS of cas: 37002-48-5

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantio- and Diastereoselective Synthesis of Functionalized Carbocycles by Cu-Catalyzed Borylative Cyclization of Alkynes with Ketones was written by Zanghi, Joseph M.;Liu, Shuang;Meek, Simon J.. And the article was included in Organic Letters in 2019.SDS of cas: 133545-16-1 This article mentions the following:

A single-pot Cu-catalyzed enantio- and diastereoselective tandem hydroboration/borylative cyclization of alkynes with ketones for the synthesis of carbocycles is reported. The reaction proceeds via desymmetrization and generates four contiguous stereocenters, including an all-C quaternary center. The method provides rapid access to [6,5]- and [5,5]-bicycles and cyclopentane products. Catalyst-controlled diastereoselectivity by selection of bisphosphine ligand is noted. Utility of the products is demonstrated by site- and chemoselective transformations that afford valuable alkenyl and allyl organoborons. In the experiment, the researchers used many compounds, for example, (R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1SDS of cas: 133545-16-1).

(R)-(6,6′-Dimethoxy-[1,1′-biphenyl]-2,2′-diyl)bis(diphenylphosphine) (cas: 133545-16-1) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.SDS of cas: 133545-16-1

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis