Category: 139139-93-8

Ishii, Masahiro; Mori, Fumiya; Tanaka, Ken published the artcile< Rhodium-Catalyzed [2+2+2] Cycloaddition of Diynes with Carbodiimides and Carbon Dioxide under Ambient Conditions>, COA of Formula: C44H40P2, the main research area is rhodium cycloaddition diyne carbodiimide carbon dioxide; carbodiimides; carbon dioxide; cycloaddition; diynes; rhodium.

It was established that a cationic rhodium(I)/H8-BINAP complex is able to catalyze a [2+2+2] cycloaddition of diynes with carbodiimides and carbon dioxide under ambient conditions. Enantioselective variants and regioselective variants of these reactions are also disclosed. Under optimized conditions the synthesis of the target compounds was achieved using N,N’-[(methane)tetrayl]bis[4-methylbenzenamine], N,N’-[(methane)tetrayl]bis[cyclohexanamine] (i.e., dicyclohexylcarbodiimide) and diynes, such as 2,2-bis(2-propynyl)propanedioic acid esters, 4-methyl-N,N-bis(2-propynyl)benzenesulfonamide. 3,3-bis(2-butynyl)-2,4-pentanedione as starting materials, bis[(1,2,5,6-η)-1,5-cyclooctadiene]rhodium tetrafluoroborate(1-) as a catalyst and 1,1′-(5,5′,6,6′,7,7′,8,8′-octahydro[1,1′-binaphthalene]-2,2′-diyl)bis[1,1-diphenylphosphine] (H8-BINAP) as a ligand.

Chemistry – A European Journal 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, 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

Hatano, Manabu; Terada, Masahiro; Mikami, Koichi published the artcile< Highly enantioselective palladium-catalyzed ene-type cyclization of a 1,6-enyne>, Quality Control of 139139-93-8, the main research area is furan vinyl methoxycarbonylmethylidene methyl preparation enantioselective; palladium catalyzed carbocyclization enyne; crystal structure vinylmethylcaboxymethylidenefuran phenylethylamine salt; asymmetric catalysis; cyclizations; enynes; palladium.

The authors developed a highly efficient palladium(II)-catalyzed ene-type carbocyclization of 1,6-enyne MeCH=C(Me)CH2OCH2CCCO2Me leading to enantiopure furan (I). This highly enantioselective catalysis is applicable for the construction of an enantioenriched quaternary chiral center. Possible mechanisms including neutral and cationic intermediate have been proposed.

Angewandte Chemie, International Edition 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, 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

Shibata, Takanori; Fujimoto, Masako; Hirashima, Hiroyuki; Chiba, Tatsuya; Endo, Kohei published the artcile< Facile synthesis of cyclic polyphenylenes by consecutive inter- and intramolecular cycloadditions of ortho-, meta-, and para-phenylene-tethered triynes>, Formula: C44H40P2, the main research area is cyclic polyphenylene synthesis phenylene tethered triyne.

Consecutive inter- and intramol. [2 + 2 + 2] cycloadditions of various phenylene-tethered triynes were comprehensively studied by using chiral rhodium catalysts. Ortho-Phenylene-tethered triynes gave chiral o,o,o,o-tetraphenylenes in high-to-excellent enantiomeric excess as dimers. Meta-Phenylene-tethered triynes gave chiral o,m,o,m-tetraphenylenes in moderate enantiomeric excess as dimers along with hexaphenylenes as trimers. This is the first synthesis of cis-o,m,o,m-tetraphenylenes; one structure was ascertained by X-ray crystal structure anal. Para-Phenylene-tethered triynes gave o,p,o,p,o,p-hexaphenylenes as trimers along with the formation of o,p,o,p,o,p,o,p-octaphenylenes as tetramers.

Synthesis published new progress about Alkynes Role: RCT (Reactant), RACT (Reactant or Reagent). 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

Kita, Yusuke; Kavthe, Rahul D.; Oda, Hiroaki; Mashima, Kazushi published the artcile< Asymmetric Allylic Alkylation of β-Ketoesters with Allylic Alcohols by Nickel/Diphosphine Catalyst>, Safety of (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is enantioselective allylic alkylation nickel diphosphine catalyst; alkylation beta ketoester allylic alc; alkylation; allylic compounds; asymmetric catalysis; enantioselectivity; nickel.

Asym. allylic alkylation of β-ketoesters with allylic alcs. catalyzed by [Ni(cod)2]/(S)-H8-BINAP was found to be a superior synthetic protocol for constructing quaternary chiral centers at the α-position of β-ketoesters. The reaction proceeded in high yield and with high enantioselectivity using various β-ketoesters and allylic alcs., without any addnl. activators. The versatility of this methodol. for accessing useful and enantioenriched products was demonstrated.

Angewandte Chemie, International Edition published new progress about Allylic alcohols Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Safety of (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

Oonishi, Yoshihiro; Hato, Yoshio; Sato, Yoshihiro published the artcile< Rhodium(I)-Catalyzed Diastereoselective Cycloisomerization of Enynes with Tethered (S)-2-Methyl-2-propanesulfinyl Imine>, Application of C44H40P2, the main research area is enyne tethered sulfinyl imine rhodium catalyst cycloisomerization; cyclic diene enantioselective diastereoselective preparation dienophile Diels Alder reaction; spiroamide diastereoselective enantioselective preparation.

The rhodium(I)-catalyzed cycloisomerization of enynes with tethered (S)-2-methyl-2-propanesulfinyl imine afforded 5- or 6-membered cyclic compounds containing exocyclic 1,3-diene moieties in a stereoselective manner. The reaction proceeded through β-hydride elimination of a 7-membered azarhodacycle intermediate, which was generated from three unsaturated bonds (i.e., alkene, alkyne, and C-N bonds) and an Rh(I) complex. The resultant cyclic compounds could be reacted with various dienophiles to afford spiroamides as single isomers through the Diels-Alder reaction.

Advanced Synthesis & Catalysis published new progress about Alkenynes Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 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

Shen, Zengming; Lu, Xiyan; Lei, Aiwen published the artcile< Highly enantioselective hydrogenation of exocyclic double bond of N-tosyloxazolidinones catalyzed by a neutral rhodium complex and its synthetic applications>, Related Products of 139139-93-8, the main research area is alkylideneoxazolidinone stereoselective hydrogenation rhodium catalyst.

A highly enantioselective synthesis of optically active N-tosyl-4-alkyl-1,3-oxazolidin-2-ones based on the asym. hydrogenation of the trisubstituted exocyclic double bond of N-tosyl-4-alkylidene-1,3-oxazolidin-2-ones under the catalysis of neutral [Rh(COD)Cl]2 and (S)-(+)-DTBM-SEGPHOS was developed. The utility of this highly enantioselective reaction was exemplified by the synthesis of optically active amino acids, amino alcs., and piperidine derivatives

Tetrahedron published new progress about Amino acids Role: SPN (Synthetic Preparation), PREP (Preparation). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Related Products 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

Nogami, Juntaro; Tanaka, Yusuke; Sugiyama, Haruki; Uekusa, Hidehiro; Muranaka, Atsuya; Uchiyama, Masanobu; Tanaka, Ken published the artcile< Enantioselective Synthesis of Planar Chiral Zigzag-Type Cyclophenylene Belts by Rhodium-Catalyzed Alkyne Cyclotrimerization>, Quality Control of 139139-93-8, the main research area is zigzag cyclophenylene belt enantioselective preparation; rhodium catalyst enantioselective cyclotrimerization heptynyl oxypropynylphenoxyphenylene oligomer; mol crystal structure racemic zigzag cyclophenylene belt; mechanism enantioselectivity cyclotrimerization heptynyl oxypropynylphenoxyphenylene; ring strain calculated zigzag cyclophenylene belt; fluorescence UV visible absorption zigzag cyclophenylene belt; dissymetry factor ECD CPL nonracemic zigzag cyclophenylene belt.

Planar chiral zigzag-type [8] and [12]cyclophenylene belts were prepared enantioselectively by rhodium-catalyzed enantioselective intramol. sequential cyclotrimerizations of a cyclic [oxypropynylbis(heptynyloxy)phenoxybis(heptynyl)phenylene] dimer and trimer. The observed enantioselectivity likely arose from the regioselective formation of a rhodacyclic intermediate from an unsym. triyne unit. The structure of the racemic zigzag [8]cyclophenylene belt was determined by X-ray crystallog.; the homochiral belts mesh with one another to form columns in the solid state, with columns of alternating chiralities. The ring strain of the zigzag [8]cyclophenylene belt was smaller than that of the corresponding armchair-type cycloparaphenylene despite its smaller ring size because of the presence of strain-relieving m-terphenyl moieties. The effect of the number of the benzene rings in the zigzag cyclophenylene belts on their UV/visible absorption and fluorescence was small because of the interruption of conjugation by the m-phenylene moieties, but the effect of bending on the absorption and emission peaks and on the absolute fluorescence quantum yield was significant. Modest anisotropy dissymmetry factors of the electronic CD and CPL spectra were observed for the zigzag [8]cyclophenylene belt.

Journal of the American Chemical Society published new progress about Circular dichroism (electronic). 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

Tanaka, Ken; Nishida, Goushi; Ogino, Masakazu; Hirano, Masao; Noguchi, Keiichi published the artcile< Enantioselective synthesis of axially chiral biaryls through rhodium-catalyzed complete intermolecular cross-cyclotrimerization of internal alkynes>, Electric Literature of 139139-93-8, the main research area is alkyne acetylenedicarboxylate cross cyclotrimerization rhodium BINAP; biaryl asym preparation; benzenetetracarboxylate preparation.

A cationic rhodium(I)/H8-BINAP complex-catalyzed complete intermol. cross-cyclotrimerization of internal alkynes with dialkyl acetylenedicarboxylates was developed. This reaction was successfully applied to enantioselective synthesis of axially chiral biaryls, e.g., I, utilizing internal alkynes bearing ortho-substituted Ph and acetoxymethyl in each terminal position. The axial chirality was constructed at the formation of benzene rings with high enantioselectivity.

Organic Letters published new progress about Alkynes Role: RCT (Reactant), RACT (Reactant or Reagent). 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Electric Literature 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

Murayama, Koichi; Shibata, Yu; Sugiyama, Haruki; Uekusa, Hidehiro; Tanaka, Ken published the artcile< Synthesis, structure, and photophysical/chiroptical properties of benzopicene-based π-conjugated molecules>, Electric Literature of 139139-93-8, the main research area is benzopicene pi conjugated hydrocarbon ladder helical structure preparation cycloaddition; cycloaddition dialkynyl binaphthalene preparation benzopicene ladder helical polycycle; crystal structure helical benzopicene fluorenone ketone.

The convenient synthesis of substituted benzopicenes and azabenzopicenes I (X = C, N; R1, R2 = H, CO2Et, alkyl, CH2CH) has been achieved by the cationic rhodium(I)/H8-BINAP or BINAP complex-catalyzed [2+2+2] cycloaddition of 1,1′-dialkynyl-2,2′-binaphthalene under mild conditions. This method was applied to the synthesis of benzopicene-based long ladder (II, R3 = C12H25) and helical (III, R4 = Ph, Bu; Y2 = O, 9-fluorenylidene) mols. The x-ray crystal structure anal. revealed that the benzopicene-based helical mol. is highly distorted and the average distance of overlapped rings is markedly shorter than that in the triphenylene-based helical mol. Photophys. and chiroptical properties of these benzopicene and azabenzopicene derivatives have also been examined With respect to photophys. properties, substituted benzopicenes and azabenzopicenes showed red shifts of absorption and emission maxima compared with the corresponding triphenylenes and azatriphenylenes. With respect to chiroptical properties, the CPL spectra of the benzopicene-based helical mol. showed two opposite peaks, and thus the value of the CPL was smaller than that of the triphenylene-based helical mol. presumably due to the presence of two chiral fluorophores.

Journal of Organic Chemistry published new progress about [2+2+2] Cycloaddition reaction. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Electric Literature 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

Tanaka, Ken; Takahashi, Yoshihiro; Suda, Takeshi; Hirano, Masao published the artcile< Synthesis of enantioenriched N-aryl-2-pyridones with chiral C-N axes by rhodium-catalyzed [2+2+2] cycloaddition of alkynes with isocyanates>, Electric Literature of 139139-93-8, the main research area is alkadiyne phenyl isocyanate stereoselective cycloaddition rhodium catalyst; pyridone stereoselective preparation.

Enantioenriched N-aryl-2-pyridones with axially chiral C-N bonds were prepared by a cationic rhodium(I)-BINAP or tol-BINAP-catalyzed enantioselective [2+2+2] cycloaddition of alkadiynes with ortho-substituted Ph isocyanates.

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, Electric Literature 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