Chiral phosphine ligands

Lavernhe, Remi’s team published research in Advanced Synthesis & Catalysis in 2020 | 152140-65-3

Advanced Synthesis & Catalysispublished new progress about Allylic alkylation catalysts, stereoselective (decarboxylative). 152140-65-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C54H42N2O2P2, Application of C54H42N2O2P2.

Lavernhe, Remi; Alexy, Eric J.; Zhang, Haiming; Stoltz, Brian M. published the artcile< Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Protected Benzoin-Derived Enol Carbonates>, Application of C54H42N2O2P2, the main research area is benzoin preparation enantioselective; allyl enol carbonate preparation decarboxylative allylic alkylation palladium catalyst; allylic alkylation; asymmetric catalysis; benzoin; palladium catalysis.

The enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted α-hydroxy acyclic enol carbonates (Z)-RC(OCO2allyl)=C(OMOM)R (R = C6H5, 2-naphthyl, 2H-1,3-benzodioxol-5-yl, etc.) providing tetrasubstituted benzoin derivatives (S)-RC(O)C(OMOM)(CH2CH=CH2)R is reported. Investigation into the transformation revealed that preparation of the starting material as a single enolate isomer is crucial for optimal enantioselectivity. The obtained alkylation products contain multiple reactive sites that can be utilized toward the synthesis of stereochem. rich derivatives

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’s team published research in Journal of the American Chemical Society in 2018-08-15 | 152140-65-3

Journal of the American Chemical Societypublished new progress about Allylic alkylation. 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].

Alexy, Eric J.; Zhang, Haiming; Stoltz, Brian M. published the artcile< Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates>, Recommanded Product: N,N’-(11R,12R)-(9,10-Dihydro-9,10-ethanoanthracene-11,12-diyl)bis[2-(diphenylphosphino)benzamide], the main research area is enol carbonate acyclic palladium phosphinooxazoline decarboxylative allylic alkylation catalyst; ketone quaternary stereoselective preparation.

The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted acyclic enol carbonates providing linear α-quaternary ketones is reported. Investigation into the reaction revealed that the use of an electron-deficient phosphinooxazoline ligand renders the enolate geometry of the starting material inconsequential, with the same enantiomer of product obtained in the same level of selectivity regardless of the starting ratio of enolates. As a result, a general method toward acyclic all-carbon quaternary stereocenters has been developed.

Yasui, Takeshi’s team published research in Advanced Synthesis & Catalysis in 2021-09-07 | 139139-93-8

Advanced Synthesis & Catalysispublished new progress about [2+2+2] Cycloaddition reaction (stereoselective). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Yasui, Takeshi; Nakazato, Yuya; Kurisaki, Koutarou; Yamamoto, Yoshihiko published the artcile< Enantioselective Construction of 5-6-5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh-Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes>, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is tricyclic cyclohexadiene lactone preparation enantioselective; enediyne cycloaddition rhodium catalyst.

Herein, a Rh-catalyzed asym. [2+2+2] cycloaddition of ene-yne-yne enediynes to generate enantio-enriched tricyclic cyclohexadienes bearing a quaternary bridgehead carbon is reported. The Rh-Phanephos complex is an appropriate catalyst for the cycloaddition of enediynes bearing an unsubstituted propiolate terminus, whereas Rh-biaryl bisphosphine catalysts, which have been widely used for asym. cycloadditions of alkynes and alkenes, are not applicable for the reaction of such enediynes. Several control experiments suggest that the reaction using the Rh-Phanephos complex exclusively proceeds via a rhodacyclopentadiene intermediate, unlike when using a Rh-biaryl bisphosphine complex that can form a rhodacyclopentadiene intermediate as well as a rhodacyclopentene intermediate in a substrate-dependent manner.

Brusoe, Andrew T’s team published research in Angewandte Chemie, International Edition in 2011 | 139139-86-9

Angewandte Chemie, International Editionpublished new progress about Allenes Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, COA of Formula: C44H40P2.

Brusoe, Andrew T.; Alexanian, Erik J. published the artcile< Rhodium(I)-Catalyzed Ene-Allene-Allene [2+2+2] Cycloadditions: Stereoselective Synthesis of Complex trans-Fused Carbocycles>, COA of Formula: C44H40P2, the main research area is eneallene allene rhodium catalyzed cycloaddition; hydrindane decalin stereoselective preparation four contiguous stereocenters; fused carbocycle stereoselective preparation.

The rhodium-catalyzed [2+2+2] cycloaddition of ene-allenes with allenes was utilized for the construction of a variety of trans-fused hydrindanes and decalins in a highly convergent manner, with three σ bonds, two rings, and up to four contiguous stereocenters generated in a regio- and stereoselective fashion.

Senda, Taichi’s team published research in Journal of Organic Chemistry in 2001-10-19 | 139139-86-9

Journal of Organic Chemistrypublished new progress about Addition reaction catalysts, stereoselective. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Formula: C44H40P2.

Senda, Taichi; Ogasawara, Masamichi; Hayashi, Tamio published the artcile< Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboron Reagents to 5,6-Dihydro-2(1H)-pyridinones. Asymmetric Synthesis of 4-Aryl-2-piperidinones>, Formula: C44H40P2, the main research area is asym synthesis arylpiperidinone; stereoselective addition organoboron pyridinone; paroxetine intermediate stereoselective preparation.

Catalytic asym. synthesis of 4-aryl-2-piperidinones was realized by asym. 1,4-addition of arylboron reagents to 5,6-dihydro-2(1H)-pyridinones in the presence of a chiral bisphosphine-rhodium catalyst. In the reaction introducing the 4-fluorophenyl group, the use of 4-fluorophenylboroxine and 1 equiv (to boron) of water at 40°C gave the highest yield of the arylation product with high enantioselectivity (98% ee). The (R)-4-(4-fluorophenyl)-2-piperidinone obtained is a key intermediate for the synthesis of (-)-Paroxetine.

Wiest, Johannes M’s team published research in Angewandte Chemie, International Edition in 2018 | 277306-29-3

Angewandte Chemie, International Editionpublished 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, Category: chiral-phosphine-ligands.

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>, Category: chiral-phosphine-ligands, 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.

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

Tetrahedronpublished 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.

Felix, Ryan J’s team published research in Nature Chemistry in 2012-05-31 | 325168-88-5

Nature Chemistrypublished new progress about [3,3]-Sigmatropic rearrangement. 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, HPLC of Formula: 325168-88-5.

Felix, Ryan J.; Weber, Dieter; Gutierrez, Osvaldo; Tantillo, Dean J.; Gagne, Michel R. published the artcile< A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes>, HPLC of Formula: 325168-88-5, the main research area is gold catalysis enantioselective cope rearrangement achiral dienes.

Since the discovery of the Cope rearrangement in the 1940s, no asym. variant of the rearrangement of achiral 1,5-dienes has emerged, despite the successes that have been achieved with its heteroatom variants (Claisen, aza-Cope, and so on). This article reports the first example of an enantioselective Cope reaction that starts from an achiral diene. The new gold(I) catalyst derived from double Cl–abstraction of ((S)-3,5-xylyl-PHANEPHOS(AuCl)2), has been developed for the sigmatropic rearrangement of alkenyl-methylenecyclopropanes. The reaction proceeds at low temperature and the synthetically useful vinylcyclopropane products are obtained in high yield and enantioselectivity. D. functional theory calculations predict that: (1) the reaction proceeds via a cyclic carbenium ion intermediate, (2) the relief of strain in the methylenecyclopropane moiety provides the thermodn. driving force for the rearrangement and (3) metal complexation of the transition-state structure lowers the rearrangement barriers.

Lipshutz, Bruce H’s team published research in Journal of the American Chemical Society in 2008-11-05 | 277306-29-3

Journal of the American Chemical Societypublished new progress about Aldol condensation catalysts, stereoselective (intramol.). 277306-29-3 belongs to class chiral-phosphine-ligands, and the molecular formula is C32H40FeP2, Computed Properties of 277306-29-3.

Lipshutz, Bruce H.; Amorelli, Benjamin; Unger, John B. published the artcile< CuH-Catalyzed Enantioselective Intramolecular Reductive Aldol Reactions Generating Three New Contiguous Asymmetric Stereocenters>, Computed Properties of 277306-29-3, the main research area is unsaturated ketone copper enantioselective intramol reductive aldol chiral phosphine; cycloalkanol stereoselective preparation; enantioselective intramol reductive aldol catalyst copper chiral phosphine.

Treatment of β,β-disubstituted-α,β-unsaturated ketones, e.g., I, bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to cycloalkanols, e.g., II, with three newly created adjacent chiral centers. Excellent de’s and ee’s are obtained for several examples studied.

Chang, Xin’s team published research in Angewandte Chemie, International Edition in 2020-05-25 | 139139-93-8

Angewandte Chemie, International Editionpublished new progress about Alkenes Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation) (bis(alkenyl)dihydrosilanes). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Related Products of 139139-93-8.

Chang, Xin; Ma, Pei-Long; Chen, Hong-Chao; Li, Chuan-Ying; Wang, Peng published the artcile< Asymmetric Synthesis and Application of Chiral Spirosilabiindanes>, Related Products of 139139-93-8, the main research area is alkenyldihydrosilane preparation rhodium catalyzed asym double hydrosilation spirocyclization; spirosilabiindane chiral preparation reaction aminophosphine; phosphoramidite spirosilabiindane chiral preparation catalyst ligand asym hydrogenation carboamination; crystal structure chiral spirosilabiindane diol derivative phosphoramidite; mol structure chiral spirosilabiindane diol derivative phosphoramidite; asymmetric catalysis; ligand design; silanes; spirocompounds; synthetic methods.

Reported here is the development of a class of chiral spirosilabiindane scaffolds by Rh-catalyzed asym. double hydrosilation, for the 1st time. Enantiopure SPSiOL (spirosilabiindane diol), a new type of chiral building block for the preparation of various chiral ligands and catalysts, was readily prepared on >10 g scale using this protocol. The potential of this new spirosilabiindane scaffold in asym. catalysis was preliminarily demonstrated by development of the corresponding monodentate phosphoramidite ligands (SPSiPhos), which were used in both a Rh-catalyzed hydrogenation and a Pd-catalyzed intramol. carboamination.