Category: 139139-93-8

Tsuchikama, Kyoji; Yoshinami, Yusuke; Shibata, Takanori published the artcile< Rhodium-complex-catalyzed [2+2+2] cycloaddition of diynes and carbonyl compounds>, Product Details of C44H40P2, the main research area is diyne carbonyl stereoselective cycloaddition rhodium BINAP catalyst; hydropyran stereoselective preparation electrocyclic ring opening; cyclopentene stereoselective preparation; hydropyrrole stereoselective preparation; hydrofuran stereoselective preparation.

A Rh-BINAP complex was used to catalyze the hetero-[2+2+2] cycloaddition of sym. 1,6-diynes and carbonyl moiety of keto esters, a diketone, and an aldehyde to give bicyclic α-pyrans, which were readily transformed into monocyclic compounds via the following electrocyclic ring opening. In the reaction of an unsym. 1,6-diyne and a 1,7-diyne, α-pyrans with a quaternary carbon stereocenter were obtained in moderate to excellent ee using a chiral rhodium catalyst.

Synlett published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Product Details of C44H40P2.

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

Hirata, Shuzo; Hara, Hyuman; Bhattacharjee, Indranil published the artcile< Phosphorescence Quenching of Heavy-Atom-Free Dopant Chromophores Triggered by Thermally Activated Triplet Exciton Diffusion of a Conjugated Crystalline Host>, Formula: C44H40P2, the main research area is phosphorescence quenching heavy atom dopant chromophore thermally activated triplet.

Persistent room-temperature phosphorescence (pRTP) from aggregated mol. crystalline materials is important for stable high-resolution afterglow imaging. However, an unclear understanding concerning the deactivation mechanism from the lowest triplet excited state (T1) precludes the development of highly efficient pRTP. Here, we report the reasons for the presence and absence of pRTP from a heavy-atom-free conjugated dopant in heavy-atom-free conjugated mol. crystals. N,N-di(9H-fluoren-2-yl)phenanthrene-3-amine (DFAP) was sep. doped into fluorene crystals and (S)-2,2′-bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalene ((S)-H8-BINAP) crystals. DFAP doped in fluorene crystals with stronger intermol. interactions did not generate RTP, while DFAP doped in (S)-H8-BINAP crystals with weaker intermol. interactions showed strong pRTP. The pRTP of DFAP doped in (S)-H8-BINAP crystals is explained by the deep confinement of the T1 of DFAP in the (S)-H8-BINAP crystals with a large T1 energy. The absence of RTP from DFAP doped in fluorene crystals is explained by the temperature dependence of phosphorescence and quantum calculations, which suggest that deactivation is mainly caused by quenching after diffusion of triplet excitons of the host crystals. The temperature dependence of the triplet-triplet annihilation-based delayed fluorescence of the fluorene crystalline host confirms that the triplet diffusion of the fluorene crystalline host deactivates the triplet excitons of DFAP.

Journal of Physical Chemistry C published new progress about Chromophores. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Formula: C44H40P2.

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

Nguyen, Qui-Hien; Guo, Shu-Min; Royal, Titouan; Baudoin, Olivier; Cramer, Nicolai published the artcile< Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C-H Arylation of Heteroarenes>, Formula: C44H40P2, the main research area is heteroarene azole palladium monooxidized bisphosphine chiral ligand enantioselective arylation; atropisomeric heterobiaryls preparation.

Atropisomeric (hetero)biaryls are motifs with increasing significance in ligands, natural products, and biol. active mols. The straightforward construction of the stereogenic axis by efficient C-H functionalization methods is extremely rare and challenging. An intermol. and highly enantioselective C-H arylation of relevant heteroarenes providing an efficient access to atropisomeric (hetero)biaryls is reported. The use of a Pd(0) complex equipped with H8-BINAPO as a chiral ligand enables the direct functionalization of a broad range of 1,2,3-triazoles and pyrazoles in excellent yields and selectivities of up to 97.5:2.5 er. The method also allows for an atroposelective double C-H arylation for the construction of two stereogenic axes with >99.5:0.5 er.

Journal of the American Chemical Society published new progress about Arylation catalysts, stereoselective. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Formula: C44H40P2.

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

Zhang, Xiaoyong; Mashima, Kazushi; Koyano, Kinko; Sayo, Noboru; Kumobayashi, Hidenori; Akutagawa, Susumu; Takaya, Hidemasa published the artcile< Synthesis of partially hydrogenated BINAP variants>, SDS of cas: 139139-93-8, the main research area is BINAP hydrogenated; crystal structure cyclohexylphosphinylbinaphthyl; mol structure cyclohexylphosphinylbinaphthyl; binaphthyl hydro atropisomeric phosphine ligand.

Three pairs of new axially dissym. diphosphine ligands, (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphino)-1,1′-binaphthyl, (R)-(+)- and (S)-(-)-2,2′-bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl and (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, have been synthesized and their absolute configurations have been determined on the basis of an x-ray anal. and CD spectra.

Tetrahedron Letters published new progress about 139139-93-8. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, SDS of cas: 139139-93-8.

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

Shibata, Takanori; Takami, Kyoko; Kawachi, Ai published the artcile< Rh-Catalyzed Enantioselective [2+2] Cycloaddition of Alkynyl Esters and Norbornene Derivatives>, Quality Control of 139139-93-8, the main research area is cyclobutene tetracyclic tricyclic asym synthesis; asym synthesis tricyclononenecarboxylate; rhodium catalyst enantioselective cycloaddition alkynyl ester norbornene.

The enantioselective [2+2] cycloaddition of alkynes possessing an ester functionality, e.g. PhCCCO2Me, and norbornene derivatives proceeded efficiently using a chiral rhodium catalyst. The resulting chiral tri- and tetracyclic cyclobutenes were obtained in moderate to high ee.

Organic Letters published new progress about [2+2] Cycloaddition reaction, stereoselective. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Quality Control of 139139-93-8.

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

Hato, Yoshio; Oonishi, Yoshihiro; Yamamoto, Yasunori; Nakajima, Kiyohiko; Sato, Yoshihiro published the artcile< Stereoselective Construction of Spiro-Fused Tricyclic Frameworks by Sequential Reaction of Enynes, Imines, and Diazoalkenes with Rh(I) and Rh(II) Catalysts>, Application of C44H40P2, the main research area is stereoselective spiro fused tricyclic compound; rhodium catalyst imine tethered enyne reaction diazoalkene.

Stereoselective construction of spiro-fused tricyclic compounds from enynes having a tethered imine with diazoalkenes was achieved by Rh(I)- and Rh(II)-catalyzed sequential reactions. This method consists of three reactions, i.e., Rh(I)-catalyzed cyclization of enynes with a tethered imine, Rh(II)-catalyzed cyclopropanation with diazoalkenes, and Cope rearrangement. Notably, the sequential reactions can be operated in one pot, in which Rh(I) and Rh(II) catalysts work in relay without any serious catalyst deactivation to afford the spirocycles in a stereoselective manner.

Journal of Organic Chemistry published new progress about Alkenynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application of C44H40P2.

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

Kusama, Tomoya; Hirata, Shuzo published the artcile< Thermo-reversible persistent phosphorescence modulation reveals the large contribution made by rigidity to the suppression of endothermic intermolecular triplet quenching>, COA of Formula: C44H40P2, the main research area is diphenylphosphino binaphthyl triplet energy phosphorescence; diffusion constant; nonradiative deactivation; persistent room-temperature phosphorescence; phase change; reorganization energy; triplet quenching.

The suppression of thermally driven triplet deactivation is crucial for efficient persistent room-temperature phosphorescence (pRTP). However, the mechanism by which triplet deactivation occurs in metal-free mol. solids at room temperature (RT) remains unclear. Herein, we report a large pRTP intensity change in a mol. guest that depended on the reversible amorphous-crystal phase change in the mol. host, and we confirm the large contribution made by the rigidity of the host in suppressing intermol. triplet quenching in the guest. (S)-(-)-2,2′-Bis(diphenylphosphino)-1,1′- binaphthyl ((S)-BINAP) was doped as a guest into a highly purified (S)- bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl ((S)-H8-BINAP) host. It was possible to reversibly form the amorphous and crystalline states of the solid by cooling to RT from various temperatures The RTP yield (Φp) originating from the (S)-BINAP was 6.7% in the crystalline state of the (S)-H8-BINAP host, whereas it decreased to 0.31% in the amorphous state. Arrhenius plots showing the rate of nonradiative deactivation from the lowest triplet excited state (T1) of the amorphous and crystalline solids indicated that the large difference in Φp between the crystalline and amorphous states was mostly due to the discrepancy in the magnitude of quenching of intermol. triplet energy transfer from the (S)-BINAP guest to the (S)-H8-BINAP host. Controlled analyses of the T1 energy of the guest and host, and of the reorganization energy of the intermol. triplet energy transfer from the guest to the host, confirmed that the large difference in intermol. triplet quenching was due to the discrepancy in the magnitude of the diffusion constant of the (S)-H8-BINAP host between its amorphous and crystalline states. Quantification of both the T1 energy and the diffusion constant of mols. used in solid materials is crucial for a meaningful discussion of the intermol. triplet deactivation of various metal-free solid materials.

Frontiers in Chemistry (Lausanne, Switzerland) published new progress about Crystallinity. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, COA of Formula: C44H40P2.

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

Williams, David R.; Shah, Akshay A. published the artcile< Total Synthesis of (+)-Ileabethoxazole via an Iron-Mediated Pauson-Khand [2 + 2 + 1] Carbocyclization>, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is ileabethoxazole total synthesis Pauson Khand carbocyclization iron; Stille cross coupling total synthesis ileabethoxazole; insertion total synthesis ileabethoxazole; asym hydride reduction copper total synthesis ileabethoxazole.

Studies describe the total synthesis of (+)-ileabethoxazole (I) using a Stille cross-coupling reaction of propargylic stannanes with 5-iodo-1,3-oxazoles to produce 1,1-disubstituted allenes. An iron-mediated [2+2+1] carbocyclization yields a novel cyclopentenone II (R = H, Me) for elaboration to I. Site-selective palladium insertion reactions allow for regiocontrolled substitutions of the heterocycle. Asym. copper hydride reductions are examined, and strategies for the formation of the central aromatic ring are discussed.

Journal of the American Chemical Society published new progress about Cyclization (Pauson-Khand [2+2+1]-carbocyclization). 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.

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

Tsuchikama, Kyoji; Kuwata, Yusuke; Shibata, Takanori published the artcile< Highly Enantioselective Construction of a Chiral Spirocyclic Structure by the [2+2+2] Cycloaddition of Diynes and exo-Methylene Cyclic Compounds>, Application In Synthesis of 139139-93-8, the main research area is chiral spirocyclic compound preparation cycloaddition diyne exo methylene ketone.

The enantioselective [2+2+2] cycloaddition of 1,6-diynes with α-methylene lactones and cyclic ketones gave various chiral spirocyclic compounds The reaction proceeded with high enantioselectivity when the rhodium-xylylBINAP complex was used as a chiral catalyst. Not only exo-methylene cyclic compounds but also exo-methylene acyclic compounds could be used as coupling partners for diynes. The present protocol provides access to a new chiral library possessing a quaternary carbon center, including a spirocyclic system.

Journal of the American Chemical Society published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Application In Synthesis of 139139-93-8.

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

Zhang, Xiaoyong; Mashima, Kazushi; Koyano, Kinko; Sayo, Noboru; Kumobayashi, Hidenori; Akutagawa, Susumu; Takaya, Hidemasa published the artcile< Synthesis of partially hydrogenated 2,2'-bis(diphenylphosphenyl)-1,1'-binaphthyl (BINAP) ligands and their application to catalytic asymmetric hydrogenation>, Recommanded Product: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is bisphosphine chiral partially hydrogenated synthesis ligand; ruthenium catalyst hydrogenation chiral phosphine ligand; asym hydrogenation ruthenium catalyst chiral phosphine; crystal structure chiral diphosphine ruthenium cation; mol structure chiral diphosphine ruthenium cation.

Three pairs of new axially dissym. bisphosphine ligands, (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphinyl)-1,1′-binaphthyl [ I, R = C6H11], (R)-(+)- and (S)-(-)-2,2′-bis(diphenylphosphinyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl [II, R = Ph], and (R)-(-)- and (S)-(+)-2,2′-bis(dicyclohexylphosphinyl)-5,5′,6,6,7,7′,8,8′-octahydro-1,1′-binaphthyl [II, R = C6H11], have been synthesized. The absolute configurations of the isomers I were determined by single-crystal x-ray diffraction of the linear 1:1 polymeric complex of (S)-(+)-2,2′-bis(dicyclohexylphosphinoyl)-1,1′-binaphthyl [III] and (2R,3R)-(-)-di-O-benzoyltartaric acid [(-)-DBT], and those of the isomers II were established on the basis of CD spectra of the phosphanes and their bisoxides. X-ray crystallog. studies of two cationic Rh1 complexes, [Rh{(S)-Cy-binap}(COD)]ClO4 [(S)-IV] and [Rh{(S)-H8-binap}(COD)]ClO4[(S)-V], revealed that complex (S)-IV possesses a disym. structure, while complex (S)-V has a pseudo-C2-symmetry and shows a significantly large dihedral angle between the two Ph rings [80.3(4)°]. The potentially of ligand II for asym. catalysis was demonstrated in RuII-catalyzed stereoselective hydrogenations of Me 2-(benzamidomethyl)-3-oxobutanoate, (in up to 92% d.e. and 99% e.e.) and geraniol (in 98% optical purity).

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999) published new progress about Crystal structure. 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.

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