Tag: M.W=800-1000

Yamamoto, Kosuke; Qureshi, Zafar; Tsoung, Jennifer; Pisella, Guillaume; Lautens, Mark published the artcile< Combining Ru-Catalyzed C-H Functionalization with Pd-Catalyzed Asymmetric Allylic Alkylation: Synthesis of 3-Allyl-3-aryl Oxindole Derivatives from Aryl α-Diazoamides>, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is ruthenium catalyst functionalization palladium asym allylic alkylation aryl diazoamide; allylaryl oxindole stereoselective preparation.

Ruthenium-catalyzed C-H functionalization was successfully combined with palladium-catalyzed asym. allylic alkylation in one pot. The novel dual-metal-catalyzed reaction provides a variety of 3-allyl-3-aryl oxindoles from the corresponding α-diazoamides in up to 99% yield with up to 85% ee. The appropriate ligand choice is important to promote the sequential reaction, avoiding undesired metal interaction or ligand exchange.

Organic Letters 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].

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

Trost, Barry M.; Thaisrivongs, David A.; Hartwig, Jan published the artcile< Palladium-Catalyzed Asymmetric Allylic Alkylations of Polynitrogen-Containing Aromatic Heterocycles>, Computed Properties of 152140-65-3, the main research area is cyclohexenylmethyl nitrogen heterocycle enantioselective preparation; enantioselective allylic alkylation cyclohexenyl cyclopentenyl mesityl ester nitrogen heterocycle; trimethylbenzoate ester leaving group enantioselective allylic alkylation reaction.

Nonracemic cyclohexenylmethyl- and cyclopentenylmethyl-substituted nitrogen heterocycles such as I are prepared in 44-93% yields and in 75->99% ee by enantioselective allylic alkylation reactions of cyclohexenyl and cyclopentenyl trimethylbenzoates with methyl-substituted nitrogen heterocycles such as 2-methylpyrazine in the presence of bis(allylpalladium chloride) and a nonracemic dibenzamidodibenzobicyclooctane ligand. Methylated nitrogen-containing aromatic heterocycles such as 2-methylpyrazine, 2-methylpyrimidine, 3-methyl-6-phenylpyridazine, 2-methylquinoxaline, and 1-benzyl-2-methylbenzimidazole are effective reactants. 5,6,7,8-Tetrahydroquinoxaline also undergoes enantioselective allylic alkylation with a cyclohexenyl trimethylbenzoate to give cyclohexenyl tetrahydroquinoxaline II in 99% yield, >99% ee, and in 81:19 diastereoselectivity. The mesityl ester, whose steric bulk prevents competitive deacylation of the electrophile from “”hard”” nucleophiles, is introduced as a new leaving group in allylic alkylation chem. In contrast to previous studies of enantioselective allylic alkylation reactions with pyridine-based substrates, no precomplexation with a Lewis acid is required before deprotonation of the nucleophiles with LiHMDS, underscoring the relative acidity of these electron-deficient nucleophiles.

Journal of the American Chemical Society published new progress about Allylic alcohols Role: RCT (Reactant), RACT (Reactant or Reagent) (esters). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Computed Properties 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

Trost, Barry M.; Michaelis, David J.; Charpentier, Julie; Xu, Jiayi published the artcile< Palladium-Catalyzed Allylic Alkylation of Carboxylic Acid Derivatives: N-Acyloxazolinones as Ester Enolate Equivalents>, COA of Formula: C54H42N2O2P2, the main research area is acylbenzoxazolinone allylic enol carbonate stereoselective preparation enantioselective rearrangement decarboxylation; alkenoyl benzoxazolinone enantioselective preparation; enantioselective rearrangement decarboxylation acylbenzoxazolinone allylic enol carbonate palladium phosphinylbenzamide.

Acylbenzoxazolinone allylic enol carbonates I [R = Me, Et, EtCH2, H2C:CHCH2, PhCH2, cyclohexyl, Cl(CH2)3, EtO2C(CH2)3, TBDPSO(CH2)3; R1 = H2C:CHCH2, H2C:CMeCH2, H2C:C(SiMe3)CH2, 2-cyclohexen-1-yl, (E)-PhCH:CHCH2; TBDPS = tert-butyldiphenylsilyl] underwent stereoselective rearrangement and decarboxylation in the presence of the nonracemic phosphinylbenzamide II (R2 = 2-MeC6H4) and tris(dibenzylidene)dipalladium chloroform solvate to give nonracemic alkanoyl benzoxazolinones III in 58-99% yields and in 79-99% ee [R = Me, Et, EtCH2, H2C:CHCH2, PhCH2, cyclohexyl, Cl(CH2)3, EtO2C(CH2)3, TBDPSO(CH2)3; R1 = H2C:CHCH2, H2C:CMeCH2, H2C:C(SiMe3)CH2, 2-cyclohexen-1-yl, (E)-PhCH:CHCH2 with minor regioisomeric impurities formed when R1 = (E)-PhCH:CHCH2]. III (R = Me; R1 = 2-methyl-2-propenyl) in 97% ee was converted stereoselectively to carboxylic acid and alc. derivatives (S)-R2CHMeCH2CMe:CH2 (R2 = HO2C, PhCH2OCO, PhCH2SCO, HOCH2) in 78-86% yields and with the products in 96-97% ee.

Angewandte Chemie, International Edition published new progress about Decarboxylation (stereoselective). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, COA of Formula: C54H42N2O2P2.

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

Trost, Barry M.; Schultz, Johnathan E.; Bai, Yu published the artcile< Development of Chemo- and Enantioselective Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of α-Nitroesters>, Name: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is acyclic nitroalkane enantioselective preparation; nitro allyl ester decarboxylative enantioselective allylic alkylation palladium catalyst; allylic alkylation; asymmetric catalysis; chemoselectivity; enantioselectivity; palladium catalysis.

We describe the development of a Pd-catalyzed decarboxylative asym. allylic alkylation of α-nitro allyl esters to afford acyclic tetrasubstituted nitroalkanes. Optimization of the reaction parameters revealed unique ligand and solvent combinations crucial for achieving chemo- and enantioselective C-alkylation of electronically challenging benzylic nitronates and sterically encumbered 2-allyl esters. Substrates were efficiently accessed in a combinatorial fashion by a cross-Claisen/ α-arylation sequence. The method provides functional group orthogonality that complements nucleophilic imine allylation strategies for α-tertiary amine synthesis.

Angewandte Chemie, International Edition published new progress about Alkanes, nitro Role: SPN (Synthetic Preparation), PREP (Preparation). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Name: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide].

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

Trost, Barry M.; Sacchi, Karna L.; Schroeder, Gretchen M.; Asakawa, Naoyuki published the artcile< Intramolecular Palladium-Catalyzed Allylic Alkylation: Enantio- and Diastereoselective Synthesis of [2.2.2] Bicycles>, Product Details of C54H42N2O2P2, the main research area is bicyclooctanedione vinyl enantioselective diastereoselective preparation; quinuclidinone vinyl enantioselective diastereoselective preparation; cyclohexenone acetoxybutenyl intramol palladium catalyzed allylic alkylation; hydroxypyridine tetrahydro methoxycarbonylbutenyl intramol palladium catalyzed allylic alkylation.

Isomeric bicyclo[2.2.2]octan-2,3-diones I and potential precursors to quinine alkaloids quinuclidin-2-ones II were prepared both enantio- and diastereoselectively via intramol. Pd-catalyzed asym. allylic alkylation of functionalized alkenyl cyclohexenone III and tetrahydropyridine IV, resp.

Organic Letters published new progress about Allylic alkylation, stereoselective (intramol.). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Product Details of C54H42N2O2P2.

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

Trost, Barry M.; Thaisrivongs, David A. published the artcile< Palladium-Catalyzed Regio-, Diastereo-, and Benzylic Allylation of 2-Substituted Pyridines>, Category: chiral-phosphine-ligands, the main research area is regioselective diastereoselective enantioselective palladium catalyst allylic alkylation pyridine.

We report a new method for the highly regio-, diastereo-, and enantioselective palladium-catalyzed allylic alkylation of 2-substituted pyridines that allows for the formation of homoallylic stereocenters containing alkyl, aryl, heteroaryl, and nitrogen substituents. When the reaction is conducted with asym. acyclic electrophiles, both linear and branched products may be obtained exclusively by selecting the appropriate regioisomeric starting material and ligand, an example of the “”memory effect.””. Deuterium-labeling studies reveal that though no such phenomenon occurs with racemic cyclic electrophiles, the chiral ligand employed reacts kinetically faster with the enantiomer of the substrate for which it is “”matched”” and yet eventually converts all “”mismatched”” substrate to product.

Journal of the American Chemical Society published new progress about Allylic alkylation. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Category: chiral-phosphine-ligands.

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

Akula, Ramulu; Doran, Robert; Guiry, Patrick J. published the artcile< Highly enantioselective formation of α-allyl-α-arylcyclopentanones via Pd-catalysed decarboxylative asymmetric allylic alkylation>, Category: chiral-phosphine-ligands, the main research area is allyl alpha arylcyclopentanone enantioselective preparation; alpha aryl beta ketoester asym allylic alkylation ANDEN Trost; allylic alkylation; asymmetric catalysis; decarboxylation; natural products; palladium.

A highly enantioselective Pd-catalyzed decarboxylative asym. allylic alkylation of cyclopentanone derived α-aryl-β-keto esters employing the (R,R)-ANDEN-Ph Trost ligand was developed. The product (S)-α-allyl-α-arylcyclopentanones, e.g., I [Ar = 2,4,6-(MeO)3C6H2, 2,6-(MeO)2C6H3, 2,4-(MeO)2C6H3, etc.] were obtained in excellent yields and enantioselectivities (up to >99.9 % ee). This represented one of the most highly enantioselective formations of an all-carbon quaternary stereogenic center reported to date. This reaction was demonstrated on a 4.0 mmol scale without any deterioration of enantioselectivity and was exploited as the key enantioselective transformation in an asym. formal synthesis of the natural product (+)-tanikolide.

Chemistry – A European Journal published new progress about Allyl group. 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Category: chiral-phosphine-ligands.

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

Ghosh, Santanu; Chaudhuri, Saikat; Bisai, Alakesh published the artcile< Catalytic Enantioselective Decarboxylative Allylations of a Mixture of Allyl Carbonates and Allyl Esters: Total Synthesis of (-)- and (+)-Folicanthine>, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is enantioselective decarboxylative allylation allyl carbonate allyl ester palladium catalyst; folicanthine total synthesis; chimonanthine calycanthine ditryptophenaline formal synthesis; alkaloids; allylation; enantioselectivity; palladium; quaternary stereocentres.

A highly enantioselective decarboxylative allylation of a mixture of enol carbonates and allyl esters has been achieved. The strategic viability of this methodol. has been demonstrated through the total synthesis of cyclotryptamine alkaloids (-)- and (+)-folicanthine and the formal total synthesis of (-)-chimonanthine, (+)-calycanthine, and (-)-ditryptophenaline.

Chemistry – A European Journal published new progress about Allylation 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].

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

Trost, Barry M.; Xu, Jiayi published the artcile< Palladium-Catalyzed Asymmetric Allylic α-Alkylation of Acyclic Ketones>, HPLC of Formula: 152140-65-3, the main research area is palladium catalyzed asym allylic alkylation acyclic ketone.

The first example of Pd-catalyzed asym. allyl alkylation of the conformationally nonrigid acyclic ketone enolates is reported with excellent yields, regioselectivity, and enantioselectivity. The double bond geometry of the allyl enol carbonates affects its reactivity, selectivity, as well as the absolute configuration of the products. An opposite enantioselectivity from what is predicted by a direct attack of the enolate on the allyl moiety of the π-ally-Pd complex was observed An alternative mechanism was proposed, which involves an inner sphere process of coordination of the enolate to Pd followed by reductive elimination.

Journal of the American Chemical Society published new progress about Absolute configuration (product). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, HPLC of Formula: 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

Alexy, Eric J.; Virgil, Scott C.; Bartberger, Michael D.; Stoltz, Brian M. published the artcile< Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones>, Application In Synthesis of 152140-65-3, the main research area is thiopyranone enantioselective decarboxylative allylic alkylation palladium reduction; acyclic stereogenic quaternary ketone enantioselective preparation; palladium enantioselective decarboxylative allylic alkylation catalyst.

A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The α-quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening β-sulfur elimination. In addition, reduction of the carbon-sulfur bonds provides access to elusive acyclic α-quaternary ketones. The alkylated products, e.g. I, were obtained in up to 92% yield and 94% enantiomeric excess.

Organic Letters published new progress about Allylic alkylation (enantioselective, decarboxylative). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Application In Synthesis 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