October 14, 2022 | Page 3 of 8 | Chiral phosphine ligands

Tsukamoto, Hirokazu’s team published research in Advanced Synthesis & Catalysis in 2019 | CAS: 210169-54-3

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.HPLC of Formula: 210169-54-3

The author of 《Palladium-Catalyzed Umpolung Type-II Cyclization of Allylic Carbonate-Aldehydes Leading to 3-methylenecycloalkanol Derivatives》 were Tsukamoto, Hirokazu; Kawase, Ayumu; Doi, Takayuki. And the article was published in Advanced Synthesis & Catalysis in 2019. HPLC of Formula: 210169-54-3 The author mentioned the following in the article:

Palladium-catalyzed umpolung type-II cyclization of allylic carbonate-aldehydes leading to 3-methylenecycloalkanol derivatives was developed [e.g., I -> II (99%)]. The formate reductant was effective for the cyclization without causing a reduction of the η3-allylpalladium intermediate. One-pot decarboxylative allylation of aldehyde-containing malonate with 2-[(acetyloxy)methyl]-2-propenyl Me carbonate followed by the cyclization of the allyl acetate-aldehyde formed in situ was also achieved. The high diastereoselectivities observed in the cyclization of branched substrates indicates that a chair-chair transition state should be involved. Based on the presumed transition state, we could predict the enantioselectivity of the cyclization using SEGPHOS as a chiral diphosphine ligand and obtain optically active alcs. in up to 95:5 er.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3HPLC of Formula: 210169-54-3) was used in this study.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Li, Qiuyu’s team published research in Journal of the American Chemical Society in 2022 | CAS: 210169-54-3

In 2022,Li, Qiuyu; Fang, Xinxin; Pan, Rui; Yao, Hequan; Lin, Aijun published an article in Journal of the American Chemical Society. The title of the article was 《Palladium-Catalyzed Asymmetric Sequential Hydroamination of 1,3-Enynes: Enantioselective Syntheses of Chiral Imidazolidinones》.Product Details of 210169-54-3 The author mentioned the following in the article:

Pd-catalyzed sequential hydroamination of readily available 1,3-enynes was reported. The redox-neutral process provides an efficient route to synthesize a broad scope of imidazolidinones, thiadiazolidines, and imidazolidines. Asym. sequential hydroamination generates a series of synthetically valuable, enantioenriched imidazolidinones. Mechanistic studies revealed that the transformation occurred via an intermol. enyne hydroamination pathway to give an allene intermediate. Subsequent intramol. hydroamination of the allene intermediate was proceeded under the Curtin-Hammett principle to provide enantioenriched imidazolidinone products. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Product Details of 210169-54-3)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Li, Xiang’s team published research in Journal of the American Chemical Society in 2018 | 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 aldehydesRecommanded Product: 210169-54-3

Recommanded Product: 210169-54-3In 2018 ,《Palladium-Catalyzed Enantioselective Intramolecular Dearomative Heck Reaction》 was published in Journal of the American Chemical Society. The article was written by Li, Xiang; Zhou, Bo; Yang, Run-Ze; Yang, Fu-Ming; Liang, Ren-Xiao; Liu, Ren-Rong; Jia, Yi-Xia. The article contains the following contents:

Enantioselective intramol. dearomative Heck reactions have been developed by Pd-catalyzed cross-coupling of aryl halides or aryl triflates with the internal C=C bond of indoles, benzofurans, pyrroles, and furans. A variety of structurally unique spiroheterocycles and benzofused heterocycles having N/O-substituted quaternary carbon stereocenters, and exocyclic olefin moieties were afforded in moderate to excellent yields with good to excellent enantioselectivities, showing a broad scope of the present protocol. A series of new BINOL- and H8-BINOL-based phosphoramidite ligands were synthesized and proved to be efficient chiral ligands in the reactions of C2-tethered substrates to form spiroheterocycles. (S)-SEGPHOS turned out to be a good ligand for the reaction delivering benzofused indolines and pyrrolines. Synthetic applications based on transformations of the exocyclic double bonds were realized without loss of enantiopurities, including hydrogenation, hydroborylation, and stereospecific ring-expanding rearrangement. In addition to this study using (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole, there are many other studies that have used (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Recommanded Product: 210169-54-3) was used in this study.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Wang, Yan’s team published research in Angewandte Chemie, International Edition in 2016 | CAS: 210169-54-3

Recommanded Product: (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2016 ,《Enantioselective Rhodium-Catalyzed Dearomative Arylation or Alkenylation of Quinolinium Salts》 was published in Angewandte Chemie, International Edition. The article was written by Wang, Yan; Liu, Yunlong; Zhang, Dongdong; Wei, Hao; Shi, Min; Wang, Feijun. The article contains the following contents:

A highly enantioselective rhodium(I)-catalyzed dearomative arylation or alkenylation of easily available N-alkylquinolinium salts is reported, thus providing an effective and practical approach to the synthesis of dihydroquinolines in up to 99% ee. This reaction tolerates a wide range of functional groups with respect to both the organic boronic acids and the quinoline starting materials. Moreover, the synthetic utility of this protocol is demonstrated in the formal asym. synthesis of bioactive tetrahydroquinoline and the total syntheses of (-)-angustureine and (+)-cuspareine. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Recommanded Product: (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole)

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Xiao, Hua’s team published research in Angewandte Chemie, International Edition in 2010 | CAS: 286454-86-2

(S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas:286454-86-2) is one of aminophosphine type ligands. An increased interest in aminophosphine type ligands used for asymmetric synthesis has been witnessed.SDS of cas: 286454-86-2 This growth in popularity of aminophosphine ligands in asymmetric synthesis is in part due to the growing number of convenient synthetic pathways leading to useful ligand sets.

《Asymmetric [3+2] Cycloadditions of Allenoates and Dual Activated Olefins Catalyzed by Simple Bifunctional N-Acyl Aminophosphines》 was published in Angewandte Chemie, International Edition in 2010. These research results belong to Xiao, Hua; Chai, Zhuo; Zheng, Chang-Wu; Yang, Ying-Quan; Liu, Wen; Zhang, Jun-Kang; Zhao, Gang. SDS of cas: 286454-86-2 The article mentions the following:

Chiral cyclopentene derivatives, e.g. I, were prepared via asym. organocatalytic [3+2] cycloaddition between allenoates, e.g. CH2:C:CHCO2Et, and dual activated olefin, e.g. II, using bifunctional N-acylaminophosphine catalysts, e.g. III.(S)-1-(Diphenylphosphino)-3,3-dimethylbutan-2-amine(cas: 286454-86-2SDS of cas: 286454-86-2) was used in this study.

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

James, Jinju’s team published research in ACS Catalysis in 2017-02-03 | 152140-65-3

ACS Catalysis published new progress about Allylic alkylation. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Electric Literature of 152140-65-3.

James, Jinju; Guiry, Patrick J. published the artcile< Highly Enantioselective Construction of Sterically Hindered α-Allyl-α-Aryl Lactones via Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation>, Electric Literature of 152140-65-3, the main research area is enantioselective preparation allyl aryl lactone; palladium catalyst decarboxylative asym allylic alkylation.

Pd-catalyzed decarboxylative asym. allylic alkylation has been developed for sterically hindered α-aryl, β-oxoallyl ester lactone substrates. Pb-mediated α-arylation of the β-oxoallyl ester was used as the key step to synthesize the substrates for catalysis in moderate to high yields. Optimization studies for decarboxylative asym. allylic alkylations (DAAA) were conducted using δ-valerolactone-derived α-aryl β-oxoallyl ester with 2,4,6-trimethoxyphenyl as the aryl substituent. Using (R,R)-ANDEN-Ph Trost as the chiral ligand, enantioselectivities of up to >99% ee and 98% ee were achieved with the six-membered and five-membered lactone substrates, resp. Bulky aryl groups containing di-ortho substitutions and naphthyl groups gave the highest enantioselectivities. This synthetic route allows for the simple modification of aryl groups, giving highly enantioselective access to important structural motifs.

ACS Catalysis published new progress about Allylic alkylation. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Electric Literature of 152140-65-3.

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

Tanaka, Ken’s team published research in Tetrahedron in 2008-06-30 | 139139-86-9

Tetrahedron 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, Recommanded Product: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Tanaka, Ken; Takahashi, Maho; Imase, Hidetomo; Osaka, Takuya; Noguchi, Keiichi; Hirano, Masao published the artcile< Enantioselective synthesis of α,α-disubstituted α-amino acids by Rh-catalyzed [2+2+2] cycloaddition of 1,6-diynes with protected dehydroamino acid>, Recommanded Product: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is enantioselective synthesis amino acid rhodium BINAP catalyst cycloaddition diyne; dehydroamino acid cycloaddition diyne catalyst rhodium BINAP.

We have determined that a cationic rhodium(I)/BINAP complex catalyzes a [2+2+2] cycloaddition of 1,6-diynes with protected dehydroamino acids, leading to protected α-amino acids bearing a quaternary carbon center in high yield with high enantioselectivity. Thus, aminoisoindolecarboxylate I (Ts = tosyl) was obtained in 96% yield and 97 ee by cycloaddition reaction of TsN(CH2CCMe)2 with AcNHC(:CH2)CO2Me using Rh(cod)2BF4/(R)-BINAP.

Burns, Alan R’s team published research in Organic Reactions (Hoboken, NJ, United States) in 2017 | 139139-86-9

Organic Reactions (Hoboken, NJ, United States) published new progress about 1,4-Addition reaction catalysts (stereoselective). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application of C44H40P2.

Burns, Alan R.; Lam, Hon Wai; Roy, Iain D. published the artcile< Enantioselective, rhodium-catalyzed 1,4-addition of organoboron reagents to electron-deficient alkenes>, Application of C44H40P2, the main research area is review enantioselective rhodium catalyzed organoboron addition electron deficient alkene.

A review. The enantioselective 1,4-addition of organometallic reagents to electron-deficient alkenes is one of the most important methods for carbon-carbon bond formation. Within this field, the rhodium-catalyzed 1,4-addition of organoboron reagents to electron-deficient alkenes occupies a prominent position owing to (1) the availability, stability, and functional group tolerance of organoboron reagents, (2) the wide range of acceptors that may be employed, (3) the ability of a broad range of structurally distinct families of chiral ligands to induce high enantioselectivities in the reactions, and (4) the usually mild and exptl. convenient conditions, which generally do not require any special precautions to exclude air or moisture.

Yang, Bo’s team published research in Angewandte Chemie, International Edition in 2020-11-23 | 277306-29-3

Angewandte Chemie, International Edition published new progress about Crystal structure. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Category: chiral-phosphine-ligands.

Yang, Bo; Yang, Wu; Guo, Yonghong; You, Lijun; He, Chuan published the artcile< Enantioselective Silylation of Aliphatic C-H Bonds for the Synthesis of Silicon-Stereogenic Dihydrobenzosiloles>, Category: chiral-phosphine-ligands, the main research area is rhodium catalyzed enantioselective silylation cyclization styrene derivative arylsilane; silicon stereogenic dihydrobenzosilole containing dehydrocholesterol preparation crystal structure; mol structure silicon stereogenic dihydrobenzosilole containing dehydrocholesterol; C(sp3)−H silylation; asymmetric catalysis; dihydrobenzosiloles; hydrosilylation; silanes.

A Rh(I)-catalyzed enantioselective silylation of aliphatic C-H bonds for the synthesis of Si-stereogenic dihydrobenzosiloles is demonstrated. This reaction involves a highly enantioselective intramol. C(sp3)-H silylation of dihydrosilanes, followed by a stereospecific intermol. alkene hydrosilylation leading to the asym. tetrasubstituted silanes. A wide range of dihydrosilanes and alkenes displaying various functional groups are compatible with this process, giving access to a variety of highly functionalized Si-stereogenic dihydrobenzosiloles in good to excellent yields and enantioselectivities.

Yoshida, Tomoka’s team published research in Angewandte Chemie, International Edition in 2015 | 139139-93-8

Angewandte Chemie, International Edition published new progress about Alkynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Electric Literature of 139139-93-8.

Yoshida, Tomoka; Tajima, Yuki; Kobayashi, Masayuki; Masutomi, Koji; Noguchi, Keiichi; Tanaka, Ken published the artcile< Rhodium-Catalyzed [3+2+2] and [2+2+2] Cycloadditions of Two Alkynes with Cyclopropylideneacetamides>, Electric Literature of 139139-93-8, the main research area is cycloheptadiene diastereoselective preparation rhodium catalyst reaction mechanism; spiro cyclohexadiene stereoselective preparation rhodium catalyst reaction mechanism; alkyne unsaturated ketone cycloaddition; asymmetric catalysis; cycloaddition; heterocycles; rhodium; synthetic methods.

A cationic rhodium(I)/H8-binap complex catalyzed the [3+2+2] cycloaddition of 1,6-diynes with cyclopropylideneacetamides which produced cycloheptadiene derivatives, e.g., I, through cleavage of cyclopropane rings. A cationic rhodium(I)/(S)-binap complex catalyzed the enantioselective [2+2+2] cycloaddition of terminal alkynes, acetylenedicarboxylates, and cyclopropylideneacetamides which produced spiro-cyclohexadiene derivatives, e.g., II, which retained the cyclopropane rings.