Category: 139139-93-8

Shibata, Takanori; Otomo, Mayumi; Endo, Kohei published the artcile< Enantioselective intramolecular [2+2+2] cycloaddition of dienynes for the construction of adjacent three chiral centers>, Synthetic Route of 139139-93-8, the main research area is dienyne enantioselective intramol cycloaddition rhodium catalyst; chiral multicyclic cyclohexene asym synthesis.

A chiral Rh catalyst realized the intramol. [2+2+2] cycloaddition of yne-ene-enes, and chiral multicyclic cyclohexenes with adjacent three chiral centers were afforded with high to excellent ee.

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

Xiao, Xiong; Yu, Zhi-Xiang published the artcile< Co-Catalyzed Asymmetric Intramolecular [3+2] Cycloaddition of Yne-Alkylidenecyclopropanes and its Reaction Mechanism>, Name: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is alkylidenecyclopropanes cobalt catalyst enantioselective cycloaddition mechanism DFT; carbocycle stereoselective preparation; alkylidenecyclopropanes; carbocycles; cobalt; homogeneous catalysis; reaction mechanisms.

Developing new transition metal-catalyzed asym. cycloadditions for the synthesis of five-membered carbocycles (FMCs) is a research frontier in reaction development due to the ubiquitous presence of chiral FMCs in various functional mols. Reported here is our discovery of a highly enantioselective intramol. [3+2] cycloaddition of yne-alkylidenecyclopropanes (yne-ACPs) to bicyclo[3.3.0]octadiene, e.g., I, and bicyclo[4.3.0]nonadiene mols. using a cheap Co catalyst and com. available chiral ligand (S)-Xyl-BINAP. This reaction avoids the use of precious Pd and Rh catalysts, which are usually the choices for [3+2] reactions with ACPs. The enantiomeric excess in the present reaction can be up to 92%. Cationic cobalt(I) species was suggested by experiments as the catalytic species. DFT calculations showed that this [3+2] reaction starts with oxidative cyclometallation of alkyne and ACP, followed by ring opening of the cyclopropyl (CP) group and reductive elimination to form the cycloadduct. This mechanism is different from previous [3+2] reactions of ACPs, which usually start from CP cleavage, not from oxidative cyclization.

Chemistry – A European Journal published new progress about [3+2] Cycloaddition reaction catalysts. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Name: (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

Tanaka, Ken; Nishida, Goushi; Wada, Azusa; Noguchi, Keiichi published the artcile< Enantioselective synthesis of axially chiral phthalides through cationic [RhI(H8-BINAP)]-catalyzed cross alkyne cyclotrimerization>, Synthetic Route of 139139-93-8, the main research area is enantioselective synthesis axially chiral phthalide cationic rhodium alkyne cyclization; crystal mol structure axially chiral chlorophenyl hydroxymethyl isobenzofuranone preparation; asym synthesis axially chiral isobenzofuranone aryl hydroxymethyl preparation.

Easy access to axially chiral phthalides that bear one or two oxymethylene functionalities is provided by an enantioselective cross alkyne cyclotrimerization in the presence of the cationic complex [RhI[(S)H8-BINAP]]+. The catalyst, [(1,2,5,6-η)-1,5-cyclooctadiene][(1S)-(5,5′,6,6′,7,7′,8,8′-octahydro[1,1′-binaphthalene]-2,2′-diyl)bis[diphenylphosphine]-P,P’]rhodium(1+) tetrafluoroborate(1-), was prepared using [(1S)-5,5′,6,6′,7,7′,8,8′-octahydro[1,1′-binaphthalene]-2,2′-diyl]bis[diphenylphosphine] and bis[(1,2,5,6-η)-1,5-cyclooctadiene]rhodium tetrafluoroborate(1-) as precursors. The axial chirality is introduced during the formation of the benzene ring with high enantioselectivity. For example, the stereoselective cyclotrimerization of 3-(2-methylphenyl)-2-propynoic acid 2-propynyl ester (I) with 2-butyne-1,4-diol diacetate gave (+)-(7R)-5,6-bis[(acetyloxy)methyl]-7-(2-methyl)-1(3H)-isobenzofuranone (II).

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

Xu, Jian-Lin; Xu, Zhe-Yuan; Wang, Zi-Lu; Ma, Wei-Wei; Sun, Xin-Yue; Fu, Yao; Xu, Yun-He published the artcile< Copper-Catalyzed Regiodivergent and Enantioselective Hydrosilylation of Allenes>, Reference of 139139-93-8, the main research area is allene preparation copper catalyzed regiodivergent enantioselective hydrosilylation; biphenylallyl phenylsilane chiral preparation crystal structure; mol structure biphenylallyl phenylsilane chiral; allylsilane linear branched chiral enantioselective preparation.

A Cu-catalyzed regiodivergent hydrosilylation of a wide range of simple allenes is reported. Linear and branched allylsilanes were formed by judicious choice of solvents. Also, branched allylsilanes were obtained with high enantioselectivity (up to 97% enantiomeric excess) with the aid of a C2-sym. bisphosphine ligand in the unprecedented asym. allene hydrosilylation.

Journal of the American Chemical Society published new progress about Allenes 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, Reference 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

Ogaki, Shuichiro; Shibata, Yu; Noguchi, Keiichi; Tanaka, Ken published the artcile< Enantioselective Synthesis of Axially Chiral Hydroxy Carboxylic Acid Derivatives by Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition>, Application of C44H40P2, the main research area is naphthalenepropynoic acid derivative diyne chiral rhodium bisphosphine catalyst cycloaddition; arylnaphthalene hydroxy carboxylic acid derivative regioselective stereoselective preparation; axially chiral arylnaphthalene regioselective stereoselective preparation.

Axially chiral hydroxy carboxylic acid derivatives were successfully synthesized with high yields and ee values by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed enantioselective [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives Axially chiral hydroxy and dihydroxy carboxylic acid derivatives, bearing the aryl group at the ortho-position of the alkoxycarbonyl group, were also synthesized with high regio- and enantioselectivity.

Journal of Organic Chemistry published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent) (derivatives). 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

Xu, Qi; Zhang, Huan; Ge, Fang-Bei; Wang, Xiao-Mei; Zhang, Peng; Lu, Chuan-Jun; Liu, Ren-Rong published the artcile< Cu(I)-Catalyzed Asymmetric Arylation of Pyrroles with Diaryliodonium Salts toward the Synthesis of N-N Atropisomers>, Computed Properties of 139139-93-8, the main research area is nitrogen atropisomer preparation enantioselective; pyrrole diaryliodonium salt asym arylation copper catalyst.

The copper(I) catalysis using a bis(phosphine) dioxide ligand could catalyze the desym. C-H arylation of prochiral bipyrroles was reported. More than 50 nitrogen-nitrogen atropisomers I [R1 = Ph, 3-ClC6H4, 2-naphthyl, etc.; R2 = Me, Et, Bn, etc.; R3 = Me, Et, i-Pr; R4 = H, Me; R1R4 = CH=CH-CH=CH; Ar = Ph, 4-MeC6H4, 3-ClC6H4, etc.] were achieved in good to excellent yields with excellent enantioselectivities (≤97% yield, ≤98% ee). The reaction proceeded under mild conditions with good functional group compatibility on arenes and diaryliodonium salts. Moreover, this principle enabled iterative arylation of the bipyrroles to enantioselectively arylate different positions during the catalysis of copper.

Organic Letters published new progress about Arylation. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Computed Properties 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

Huang, Yu-Hao; Wu, Yichen; Zhu, Zile; Zheng, Sujuan; Ye, Zihang; Peng, Qian; Wang, Peng published the artcile< Enantioselective Synthesis of Silicon-Stereogenic Monohydrosilanes by Rhodium-Catalyzed Intramolecular Hydrosilylation>, Product Details of C44H40P2, the main research area is enantioselective regioselective preparation stereogenic cyclic monohydrosilane oxasilacycle; rhodium catalyzed intramol hydrosilylation; mol structure calculation cyclic monohydrosilane oxasilacycle; asymmetric synthesis; dihydrosilanes; hydrosilylation; monohydrosilane; rhodium.

Enantiopure monohydrosilanes are versatile chiral reagents for alc. resolution and mechanistic investigation. Herein, authors have demonstrated the asym. synthesis of monohydrosilanes via an intramol. hydrosilylation strategy. This protocol is suitable for the synthesis of five- and six-membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo-, regio-, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh-catalyzed intramol. asym. hydrosilylation reaction might proceed via a Chalk-Harrod mechanism, and the enantio-determining step was predicted to be oxidative addition of Si-H bond.

Angewandte Chemie, International Edition published new progress about Crystal structure. 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

Hayashi, Tamio; Kawai, Masahiro; Tokunaga, Norihito published the artcile< Asymmetric synthesis of diarylmethyl amines by rhodium-catalyzed asymmetric addition of aryl titanium reagents to imines>, Name: (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is arylsulfonyl arylimine aryltitanium asym addition rhodium; arylamine arylsulfonyl stereoselective preparation desulfonylation; amine diarylmethyl stereoselective preparation.

Rhodium/chiral phosphine-catalyzed asym. addition of aryltitanium triisopropoxides to N-arylidene sulfonamides (Ar1CH=NSO2Ar2) yielded diarylmethyl arylsulfonamides, e.g., I, enantioselectively. A rational tuning of the arene sulfonamide moiety (by introducing iso-Pr groups onto the Ph ring) brought about high enantioselectivity in the reaction. Desulfonylation of the diarylmethyl arylsulfonamides yielded chiral diarylmethyl amines, e.g., II.

Angewandte Chemie, International Edition published new progress about Addition reaction catalysts, stereoselective. 139139-93-8 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Name: (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

Yoshizaki, Soichi; Nakamura, Yu; Masutomi, Koji; Yoshida, Tomoka; Noguchi, Keiichi; Shibata, Yu; Tanaka, Ken published the artcile< Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of 1,6-Enynes with Cyclopropylideneacetamides>, Reference of 139139-93-8, the main research area is asym cycloaddition enyne cyclopropylideneacetamide rhodium catalyst.

It has been established that a cationic rhodium(I)/(S)-H8-BINAP complex catalyzes the asym. [2+2+2] cycloaddition of 1,6-enynes with cyclopropylideneacetamides to produce spirocyclohexenes in excellent enantioselectivity with retaining cyclopropane rings. E.g., in presence of [Rh(cod)2]BF4 and (S)-H8-BINAP, [2+2+2] cycloaddition of MeCCCH2NTsCH2CMe:CH2 and N-methyl-N-phenylcyclopropylideneacetamide gave 69% I (>99%ee).

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

Batuecas, Maria; Luo, Junfei; Gergelitsova, Ivana; Kramer, Katrina; Whitaker, Daniel; Vitorica-Yrezabal, Inigo J.; Larrosa, Igor published the artcile< Catalytic Asymmetric C-H Arylation of (η6-Arene)Chromium Complexes: Facile Access to Planar-Chiral Phosphines>, Safety of (S)-(-)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is catalytic asym arylation arene chromium complex mechanism; crystal structure mol planar chiral phosphine preparation.

A catalytic asym. direct C-H arylation of (η6-arene)chromium complexes to obtain planar-chiral compounds is reported. The use of the hemilabile ligand H8-BINAP(O) is key to providing high enantioselectivity in this transformation. We show that this methodol. opens the door to the synthesis of a variety of planar-chiral chromium derivatives which can be easily transformed into planar chiral mono- or diphosphines. Mechanistic studies, including synthesis and characterization of Pd and Ag complexes and their detection in the reaction mixture, suggest a Pd-catalyzed/Ag-promoted catalytic system where Ag carries out the C-H activation step.

ACS Catalysis published new progress about Arylation, stereoselective. 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