Category: 277306-29-3

Brawn, Ryan A.; Guimaraes, Cristiano R. W.; McClure, Kim F.; Liras, Spiros published the artcile< Enantioselective Hydroarylation of Bridged [3.2.1] Heterocycles: An Efficient Entry into the Homoepibatidine Skeleton>, Formula: C32H40FeP2, the main research area is homoepibatidine analog preparation enantioselective hydroarylation.

Achiral [3.2.1] bridged heterocycles containing a bridging amide can undergo enantioselective hydroarylation reactions under rhodium(I) catalysis. These reactions proceed in high yield and enantioselectivity in most cases, under mild reaction conditions and using com. available Josiphos ligands. The phosphine ligand structure and the protecting group on the nitrogen both have significant effects on the selectivity and yield of the reactions. E.g., the homoepibatidine oxa analog I was prepared

Organic Letters published new progress about Enantioselective synthesis. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Formula: 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

Loh, Charles C. J.; Schmid, Matthias; Webster, Robert; Yen, Andy; Yazdi, Shabnam K.; Franke, Patrick T.; Lautens, Mark published the artcile< Rhodium-Catalyzed Asymmetric Cycloisomerization and Parallel Kinetic Resolution of Racemic Oxabicycles>, Synthetic Route of 277306-29-3, the main research area is racemic oxabicyclic alkene rhodium asym cycloisomerization kinetic resolution catalyst; alkenes; heterocycles; isomerization; kinetic resolution; rhodium.

While desymmetrizations by intermol. asym. ring-opening reactions of oxabicyclic alkenes with various nucleophiles have been reported over the past two decades, the demonstration of an intramol. variant is unknown. Reported herein is the first rhodium-catalyzed asym. cycloisomerization of meso-oxabicyclic alkenes tethered to bridgehead nucleophiles, thus providing access to tricyclic scaffolds through a myriad of enantioselective C-O, C-N, and C-C bond formations. Moreover, we also demonstrate a unique parallel kinetic resolution, whereby racemic oxabicycles bearing two different bridgehead nucleophiles can be resolved enantioselectively.

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

Kharlamova, Alisa D.; Abel, Anton S.; Averin, Alexei D.; Maloshitskaya, Olga A.; Roznyatovskiy, Vitaly A.; Savelyev, Evgenii N.; Orlinson, Boris S.; Novakov, Ivan A.; Beletskaya, Irina P. published the artcile< Mono- and diamination of 4,6-dichloropyrimidine, 2,6-dichloropyrazine and 1,3-dichloroisoquinoline with adamantane-containing amines>, Related Products of 277306-29-3, the main research area is heteroaryl substituted adamantane containing amine preparation; dichloropyrimidine dichloropyrazine dichloroisoquinoline adamantane containing amine amination palladium catalyst; Pd catalysis; adamantane; amination; amines; isoquinoline; pyrazine; pyrimidine.

N-heteroaryl substituted adamantane-containing amines, e.g., I were of substantial interest for their perspective antiviral and psychotherapeutic activities. Chlorine atom at alpha-position of N-heterocycles was substituted by amino group using convenient nucleophilic substitution reactions with a series of adamantylalkylamines. The prototropic equilibrium in these compounds was studied using NMR spectroscopy. The introduction of second amino substituent in 4-amino-6-chloropyrimidine, 2-amino-chloropyrazine and 1-amino-3-chloroisoquinoline was achieved using Pd(0) catalysis.

Molecules published new progress about Activation energy. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Related Products 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

Feng, Yuting; Viereck, Peter; Li, Shi-Guang; Tsantrizos, Youla S. published the artcile< Rh(I)-catalyzed asymmetric transfer hydrogenation of α-enamidophosphonates to α-aminophosphonates>, Electric Literature of 277306-29-3, the main research area is rhodium catalyst stereoselective transfer hydrogenation enamidophosphonate mechanism; amino phosphonate preparation stereoselective library.

An asym. Rh-catalyzed transfer hydrogenation was developed for the conversion of α-enamidophosphonates to α-aminophosphonates (α-APs) using isopropanol as the hydride donor. This methodol. is amenable to a broad substrate scope. A library of structurally diverse α-APs was synthesized in moderate to good yield and enantiomeric excess, having a methylene moiety at Cβ and aryl, heteroaryl or alkyl side chains.

Tetrahedron published new progress about Enantioselective synthesis. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Electric Literature 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

Lautens, Mark; Fagnou, Keith; Yang, Dingqiao published the artcile< Rhodium-Catalyzed Asymmetric Ring Opening Reactions of Oxabicyclic Alkenes: Application of Halide Effects in the Development of a General Process>, Category: chiral-phosphine-ligands, the main research area is alkene oxabicyclic rhodium catalyzed asym ring opening nucleophile; naphthalenol dihydro asym synthesis; halide effect asym ring opening oxabicyclic alkene.

The halide effects in the rhodium-catalyzed asym. ring opening reaction of oxabicyclic alkenes, e.g. I, with various nucleophiles to give the corresponding dihydronaphthalenols, e.g. II [R = Et2N, 4-MeOC6H4NH, 4-methylpiperazin-1-yl, 3-indolyl, (MeO2C)2CH, 2-FC6H4O, etc.], are demonstrated. By employing halide and protic additives, the catalyst poisoning effect of aliphatic amines is reversed allowing the nucleophile to react in high yield and ee. Second, by simply changing the halide ligand on the rhodium catalyst from chloride to iodide, the reactivity and enantioselectivity of reactions employing an aromatic amine, malonate or carboxylate nucleophile are dramatically improved. Third, through the application of halide effects and more forcing reaction conditions, less reactive oxabicycle [2.2.1] substrates react to generate synthetically useful enantioenriched cyclohexenol products. Application of these new conditions to the more reactive oxabenzonorbornadiene I permits the reaction to be run with very low catalyst loadings (0.01 mol %).

Journal of the American Chemical Society published new progress about Alcohols, chiral Role: SPN (Synthetic Preparation), PREP (Preparation). 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

Tsukamoto, Hirokazu; Suzuki, Risako; Kondo, Yoshinori published the artcile< Revisiting Benzenesulfonyl Linker for the Deoxygenation and Multifunctionalization of Phenols>, Computed Properties of 277306-29-3, the main research area is arene preparation solid phase; aryl amine thioether cycloheptanone preparation solid phase; biaryl preparation solid phase; reductive cleavage resin bound aryl sulfonate palladium catalyst; coupling reaction resin bound aryl sulfonate palladium nickel catalyst; benzenesulfonyl linker deoxygenation functionalization phenol derivative preparation; benzenesulfonic benzenesulfonyl linker deoxygenation functionalization phenol derivative preparation.

Arenes are prepared by sulfonylation of phenols with a resin-bound benzenesulfonyl chloride followed by palladium- and nickel-catalyzed reductive cleavage and coupling reactions to yield arenes, benzamides, aryl amines, biaryls, aryl thioethers, and an arylcycloheptanone. The effect of changes of ligand and palladium catalyst on the palladium-catalyzed reductive cleavage of 4-tosyloxyacetanilide to acetanilide is studied as a test case for the solid-phase reductive cleavage reactions.

Journal of Combinatorial Chemistry published new progress about Aromatic hydrocarbons Role: SPN (Synthetic Preparation), PREP (Preparation). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Computed Properties 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

Yen, Andy; Choo, Ken-Loon; Yazdi, Shabnam K.; Franke, Patrick T.; Webster, Robert; Franzoni, Ivan; Loh, Charles C. J.; Poblador-Bahamonde, Amalia I.; Lautens, Mark published the artcile< Rhodium-Catalyzed Enantioselective Isomerization of meso-Oxabenzonorbornadienes to 1,2-Naphthalene Oxides>, Application In Synthesis of 277306-29-3, the main research area is epoxynaphthalene enantioselective preparation; methoxy hydronaphthalenol enantioselective preparation; rhodium phenylphosphinoferrocenylethylphosphine catalyst enantioselective isomerization oxabicycloheptenedimethanol ester benzyl ether; enantioselective isomerization ring opening oxabicycloheptene methanol rhodium phenylphosphinoferrocenylethylphosphine catalyst; mechanism stereoselectivity isomerization ring opening oxabicycloheptene rhodium phenylphosphinoferrocenylethylphosphine catalyst; acetoxymethyl bromobenzyloxymethyl epoxynaphthalene mol crystal structure; allylic compounds; asymmetric catalysis; enantioselectivity; isomerization; rhodium.

In the presence of Rh(cod)2BF4 and nonracemic diphenylphosphinoferrocenylethylphosphines, oxabicycloheptenedimethanol esters and dibenzyl ethers such as I underwent enantioselective isomerization to yield nonracemic 1,2-epoxynaphthalenes such as II in 53-99% yields and in 95->99% ee. In the presence of Rh(cod)2BF4 and a nonracemic diphenylphosphinoferrocenylethylphosphine, I and II underwent ring opening or tandem isomerization and ring opening reactions to yield methoxydihydronaphthalenols such as III. DFT calculations were performed to account for the stereoselectivities of the isomerization and ring opening reactions; ring-opening reactions of bridgehead disubstituted oxabicyclic alkenes proceed through the intermediacy of 1,2-epoxynaphthalenes and may indicate a kinetically and thermodynamically favored reductive elimination as the origin for the observed enantioselectivities. The structures of II and of a bis(bromobenzyloxymethyl) 1,2-epoxynaphthalene were determined by X-ray crystallog.

Angewandte Chemie, International Edition published new progress about Aralkyl alcohols Role: SPN (Synthetic Preparation), PREP (Preparation). 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

Loh, Charles C. J.; Fang, Xiang; Peters, Brendan; Lautens, Mark published the artcile< Benzylic Functionalization of Anthrones via the Asymmetric Ring Opening of Oxabicycles Utilizing a Fourth-Generation Rhodium Catalytic System>, Electric Literature of 277306-29-3, the main research area is anthracene anthracenone anthrone preparation; asymmetric catalysis; dearomatization; oxabicycles; rhodium; ring opening reactions.

While anthrones exist as privileged scaffolds in bioactive mols., the enantioselective functionalization of anthrones is surprisingly scarce in the literature, with no asym. transition metal catalyzed example to date. Herein, the authors report the first asym. transition metal catalyzed benzylic functionalization of anthrones through the rhodium(I) catalyzed desymmetrization of oxabicyclic compounds As previously developed rhodium(I) systems were found to be unsuitable for this substrate, a new robust fourth-generation [Rh(cod)OH]2 based catalytic system was developed to address synthetic challenges in this protocol. Under optimized conditions the synthesis of the target compounds was achieved using bis[(1,2,5,6-η)-1,5-cyclooctadiene]di-μ-hydroxydirhodium and (2R)-1-[(1R)-1-[bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene [i.e., (R,S)-PPF-tBu2, [(R)-1-[(S)-2-(Di-tert-butylphosphino)ferrocenyl]ethyl]diphenylphosphine, JOSIPHOS SL-J 0002-1] as catalyst-ligand combination. Starting materials included 9(10H)-anthracenone derivatives and 1,4-dihydro-1,4-epoxynaphthalene derivatives The title compounds thus formed included [(hydroxy)naphthalenyl]anthracenone derivatives

Chemistry – A European Journal published new progress about Anthracenes Role: RCT (Reactant), RACT (Reactant or Reagent). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Electric Literature 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

Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent published the artcile< Asymmetric Hydrogenation of 3-Substituted Pyridinium Salts>, Category: chiral-phosphine-ligands, the main research area is pyridinium salt asym hydrogenation; asymmetric catalysis; homogeneous catalysis; hydrogenation; pyridines; reaction mechanisms.

The use of an equivalent amount of an organic base leads to high enantiomeric excess in the asym. hydrogenation of N-benzylated 3-substituted pyridinium salts into the corresponding piperidines. Indeed, in the presence of Et3N, a Rh-JosiPhos catalyst reduced a range of pyridinium salts with ee values up to 90%. The role of the base was elucidated with a mechanistic study involving the isolation of the various reaction intermediates and isotopic labeling experiments Addnl., this study provided some evidence for an enantiodetermining step involving a dihydropyridine intermediate.

Chemistry – A European Journal published new progress about Bases Role: RGT (Reagent), RACT (Reactant or Reagent). 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; Boeing, Christian; Lautens, Mark published the artcile< Reagent-controlled regiodivergent resolution of unsymmetrical oxabicyclic alkenes using a cationic rhodium catalyst>, Related Products of 277306-29-3, the main research area is dihydronaphthalenol derivative asym preparation; oxabenzonorbornene derivative preparation nucleophile ring opening reaction rhodium; rhodium asym ring opening reaction catalyst.

A Rh(I) catalyzed regiodivergent addition of heteroatom nucleophiles to racemic oxabicyclic alkenes produces good yields of regioisomeric products each in high ee. Powerful reagent control is demonstrated, as the inherent reactivity of the substrate is completely dominated by the chiral catalyst complex, which is shown to require the use of cationic Rh(I). The process affords rapid access to multiple 1,2-dihydronaphthalene products in high enantioselectivity from simple starting materials.

Journal of the American Chemical Society published new progress about Crystal structure. 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Related Products 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