Category: 277306-29-3

Ruchelman, Alexander L.; Connolly, Terrence J. published the artcile< Enantioselective synthesis of the apremilast aminosulfone using catalytic asymmetric hydrogenation>, SDS of cas: 277306-29-3, the main research area is enantioselective apremilast aminosulfone catalytic asym hydrogenation.

Celgene’s Otezla (apremilast) is the first and only PDE4 inhibitor approved by the US FDA for the treatment of plaque psoriasis and psoriatic arthritis. Apremilast has been historically prepared via resolution to obtain the enantioenriched aminosulfone intermediate. Herein we have investigated the use of catalytic asym. hydrogenation for the enantioselective synthesis of the key aminosulfone intermediate in order to identify a higher yielding and greener synthesis route. Asym. reduction of the enamine 3-EtO-4-MeOC6H3C(NH2):CHSO2Me and the ketone 3-EtO-4-MeOC6H3COCH2SO2Me both proceeded with high selectivities, generating their resp. products with >95% ee.

Tetrahedron: Asymmetry published new progress about Enantioselective synthesis. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, SDS of cas: 277306-29-3.

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

Lautens, Mark; Fagnou, Keith; Taylor, Mark published the artcile< Rhodium-catalyzed asymmetric ring opening of oxabicyclic alkenes with phenols>, SDS of cas: 277306-29-3, the main research area is oxabicyclic alkene asym ring opening phenol; rhodium asym ring opening oxabicyclic alkene; stereoselective enantioselective aryloxydihydronaphthalenol preparation.

The scope of the rhodium-catalyzed asym. ring opening reaction of oxabenzonorbornadiene has been extended to include phenolic nucleophiles XC6H4OH (X = 4-F, 4-Cl, 4-Br, 4-I, 4-MeCO, 4-F3C, 4-Me, 4-NC, 2-Br, 3-Br). The enantioenriched, functionalized dihydronaphthalene products, e.g., aryloxydihydronaphthalenol I, are highly valuable intermediates for which no other practical methods of preparation are available. Using [Rh(CO)2Cl]2 as the rhodium source and ferrocene II as the diphosphine ligand allows the use of less reactive o-halophenols in the stereoselective ring opening reaction. The utility of these products has been demonstrated through their application in the synthesis of benzofuran polycyclic materials, e.g, III.

Organic Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, SDS of cas: 277306-29-3.

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

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.

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.

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

Webster, Robert; Boyer, Alistair; Fleming, Matthew J.; Lautens, Mark published the artcile< Practical Asymmetric Synthesis of Bioactive Aminotetralins from a Racemic Precursor Using a Regiodivergent Resolution>, Name: (2S)-1-[(1S)-1-[Bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene, the main research area is oxabicyclic alkene chiral rhodium catalyst amine ring opening; aminotetralin stereoselective preparation regiodivergent resolution; rotigotine stereoselective preparation.

Catalyst-controlled asym. ring opening of racemic oxabicyclic alkene I leads to two readily separable regioisomeric products, both in excellent ee. A cationic Rh catalyst, with added NH4BF4 to modulate reactivity, was required to obtain synthetically useful yields. The utility of each substituted aminotetralin product has been demonstrated by their conversion to the biol. relevant mols. Rotigotine and (S)-8-OH-DPAT in a highly efficient and practical manner.

Organic Letters published new progress about Chiral resolution (regiodivergent). 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.

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

Lautens, M.; Fagnou, K. published the artcile< Rhodium-catalyzed asymmetric ring opening reactions with carboxylate nucleophiles>, Product Details of C32H40FeP2, the main research area is stereoselective ring opening oxabenzonorbornadiene carboxylate; rhodium stereoselective ring opening oxabenzonorbornadiene carboxylate; epoxynaphthalene stereoselective ring opening carboxylate.

An asym. ring opening reaction of oxabenzonorbornadiene with carboxylate nucleophiles to generate enantiomerically enriched naphthalene-derived products containing an allylic carboxylate moiety was developed. These reactions occur in good yield and excellent enantioselectivity (>90% ee). The allylic carboxylate functionality was found to be stable towards reaction with the rhodium catalyst under the reaction conditions. In order to obtain these results, two advancements were required. First, the use of protic additives was necessary for good reactivity. Second, the exchange of the halide ligand on the catalyst from chloride to iodide was required to obtain high ee.

Tetrahedron published new progress about Nucleophiles. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Product Details of C32H40FeP2.

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

Lipshutz, Bruce H.; Servesko, Jeff M. published the artcile< CuH-catalyzed asymmetric conjugate reductions of acyclic enones>, SDS of cas: 277306-29-3, the main research area is enone conjugate copper catalyzed stereoselective reduction; alkanone asym synthesis.

A CuH-catalyzed asym. conjugate reduction of acyclic enones is reported. The reduction of enones was carried out with a catalytic amount of triphenylphosphine-copper hydride, in the presence of a chiral ligand, to afford alkanones, e.g. I, in high yields and enantiomeric excess.

Angewandte Chemie, International Edition published new progress about Aliphatic ketones Role: SPN (Synthetic Preparation), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, SDS of cas: 277306-29-3.

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

Tsui, Gavin C.; Lautens, Mark published the artcile< Rhodium(I)-Catalyzed Domino Asymmetric Ring Opening/Enantioselective Isomerization of Oxabicyclic Alkenes with Water>, Application of C32H40FeP2, the main research area is rhodium catalyzed domino asym ring opening isomerization oxabicycloalkene water; hydroxytetralone enantioselective preparation.

Enantio-enriched 2-hydroxy-1-tetralones are formed from oxabicyclic alkenes through a novel RhI-catalyzed domino reaction. The proposed mechanism involves water-induced asym. ring opening to generate chiral trans-1,2-diol intermediates and subsequent enantioselective isomerization (I → II → III).

Angewandte Chemie, International Edition published new progress about Bicyclic compounds Role: RCT (Reactant), RACT (Reactant or Reagent). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Application of C32H40FeP2.

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

Wiest, Johannes M.; Conner, Michael L.; Brown, M. Kevin published the artcile< Synthesis of (-)-Hebelophyllene E: An Entry to Geminal Dimethyl-Cyclobutanes by [2+2] Cycloaddition of Alkenes and Allenoates>, Application In Synthesis of 277306-29-3, the main research area is hebelophyllene E sesquiterpene lactone preparation relative configuration; alkene catalytic enantioselective cycloaddition allenoate; chiral geminal dimethylcyclobutane derivatives preparation diastereoselective reduction; oxazaborolidine catalyst enantioselective cycloaddition alkene allenoate; cycloaddition; enantioselectivity; natural products; small ring systems; total synthesis.

The first synthesis of hebelophyllene E (I) is presented, along with assignment of its previously unknown relative configuration through synthesis of epi-ent-hebelophyllene E. Development of a catalytic enantioselective [2+2] cycloaddition of alkenes and allenoates provides access to the required chiral geminal dimethylcyclobutanes. Key to its success is the identification of a novel oxazaborolidine catalyst which promotes the cycloaddition in high enantioselectivities with good functional-group tolerance (9 examples, up to 97:3 e.r.). Thus, a late-stage cycloaddition using a fully functionalized alkene, followed by a diastereoselective reduction allows a concise entry to this class of natural products.

Angewandte Chemie, International Edition published new progress about [2+2] Cycloaddition reaction (enantioselective, of alkenes and allenoates). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Application In Synthesis of 277306-29-3.

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

Pozo, Juan del; Zhang, Shaochen; Romiti, Filippo; Xu, Shibo; Conger, Ryan P.; Hoveyda, Amir H. published the artcile< Streamlined Catalytic Enantioselective Synthesis of α-Substituted β,γ-Unsaturated Ketones and Either of the Corresponding Tertiary Homoallylic Alcohol Diastereomers>, Quality Control of 277306-29-3, the main research area is enantioselective synthesis substituted unsaturated ketone nitrile allene; tertiary homoallylic alc diastereomer preparation anti HIV agent transformation.

A widely applicable, practical, and scalable strategy for efficient and enantioselective synthesis of β,γ-unsaturated ketones that contain an α-stereogenic center is disclosed. Accordingly, aryl, heteroaryl, alkynyl, alkenyl, allyl, or alkyl ketones that contain an α-stereogenic carbon with an alkyl, an aryl, a benzyloxy, or a siloxy moiety can be generated from readily available starting materials and by the use of com. available chiral ligands in 52-96% yield and 93:7 to >99:1 enantiomeric ratio. To develop the new method, conditions were identified so that high enantioselectivity would be attained and the resulting α-substituted NH-ketimines, wherein there is strong C=N → B(pin) coordination, would not epimerize before conversion to the derived ketone by hydrolysis. It is demonstrated that the ketone products can be converted to an assortment of homoallylic tertiary alcs. in 70-96% yield and 92:8 to >98:2 dr-in either diastereomeric form-by reactions with alkyl-, aryl-, heteroaryl-, allyl-, vinyl-, alkynyl-, or propargyl-metal reagents. The utility of the approach is highlighted through transformations that furnish other desirable derivatives and a concise synthesis route affording more than a gram of a major fragment of anti-HIV agents rubriflordilactones A and B and a specific stereoisomeric analog.

Journal of the American Chemical Society published new progress about Alcohols, homoallylic Role: PRP (Properties), SPN (Synthetic Preparation), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Quality Control of 277306-29-3.

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

Evans, Sandra; Faller, J. W.; Parr, Jonathan published the artcile< Half-sandwich complexes of ruthenium, rhodium and iridium with a chiral bisphosphine monoselenide>, Product Details of C32H40FeP2, the main research area is ruthenium rhodium iridium half sandwich chiral ferrocenylphosphine selenide chelate; chiral diphosphine mono selenide ligand half sandwich chelate preparation; bidentate chiral diphenylphosphino ferrocenyl phosphine selenide half sandwich complex; crystal structure bidentate chiral diphosphine monoselenide half sandwich chelate; mol structure bidentate chiral diphosphine monoselenide half sandwich chelate.

Neutral and cationic half-sandwich complexes of ruthenium, rhodium and iridium with chiral [(S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyl]di-t-butylphosphine selenide (L, 1) were prepared and characterized. Monoselenation of the com. available chiral bisphosphine afforded potentially bidentate, first enantiomerically pure chiral bisphosphine monoselenide ligand 1, which was reacted with metal half-sandwich dichlorides to give monodentate neutral complexes [Cp*M(L-κP)Cl2] (Cp* = η5-C5Me5; 2, 3; M = Rh, Ir) and [(η6-p-cymene)Ru(L-κP)Cl2] (4). Reaction of 2-4 with NaSbF6 gave cationic complexes [Cp*M(L-κP,κS)Cl]SbF6 (5, 6) and [(η6-cymene)Ru(L-κP,κS)Cl]SbF6 (7), resp., in which the ligand L is bound in a bidentate P,S-mode. The complexes 2-7 were characterized spectroscopically and, for complexes 3, 7 and [Cp*Ir(L-κP,κS)Cl]ClO4 (6′) the crystal structures are reported. The chirality of the ligand influences and controls the metal-centered chirality yielding one of two possible chelate complexes with high diastereoselectivity.

Journal of Organometallic Chemistry published new progress about Bidentate ligands Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation) (complexation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Product Details of C32H40FeP2.

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