M.W=600-700| Page 14 of 16 | Chiral phosphine ligands

Wang, Duo-Sheng’s team published research in Chemical Science in 2011-04-30 | 139139-86-9

Chemical Science published new progress about Diastereoselective synthesis. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Computed Properties of 139139-86-9.

Wang, Duo-Sheng; Tang, Jie; Zhou, Yong-Gui; Chen, Mu-Wang; Yu, Chang-Bin; Duan, Ying; Jiang, Guo-Fang published the artcile< Dehydration triggered asymmetric hydrogenation of 3-(α-hydroxyalkyl)indoles>, Computed Properties of 139139-86-9, the main research area is stereoselective hydrogenation hydroxyalkyl indole reactant alkylindoline preparation; palladium catalyzed asym hydrogenation hydroxyalkyl indole reactant; hydroxyalkyl indole preparation formylation Grignard addition indole reactant.

Highly enantioselective hydrogenation of 3-(α-hydroxyalkyl)indoles promoted by a Bronsted acid for dehydration to form a vinylogous iminium intermediate in situ was developed with Pd(OCOCF3)2/(R)-H8-BINAP as catalyst with up to 97% ee. This methodol. provides an efficient and rapid access to chiral 2,3-disubstituted indolines, e.g. I (R1 = 5-F, 7-Me, R2 = H; R1 = H, R2 = 2-Me, 4-MeO, 4-F).

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

Fernandez, Marti’s team published research in Advanced Synthesis & Catalysis in 2016 | 139139-86-9

Advanced Synthesis & Catalysis published new progress about Alkadiynes 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.

Fernandez, Marti; Parera, Magda; Parella, Teodor; Lledo, Agusti; Le Bras, Jean; Muzart, Jacques; Pla-Quintana, Anna; Roglans, Anna published the artcile< Rhodium-Catalyzed [2+2+2] Cycloadditions of Diynes with Morita-Baylis-Hillman Adducts: A Stereoselective Entry to Densely Functionalized Cyclohexadiene Scaffolds>, COA of Formula: C44H40P2, the main research area is cyclohexadiene scaffold enantioselective preparation; diyne Morita Baylis Hillman adduct enantioselective cycloaddition rhodium catalyst.

A rhodium-catalyzed asym. synthesis of 5,5-disubstituted cyclohexa-1,3-dienes has been achieved by [2+2+2] cycloaddition reactions between diynes and Morita-Baylis-Hillman (M-B-H) adducts as unsaturated substrates. Products containing two adjacent chiral centers (quaternary and tertiary, resp.) were obtained with complete diastereoselectivity and high enantioselectivity (84-97%) through a kinetic resolution of the M-B-H adduct. Furthermore, these highly substituted cyclohexadienes reacted with dienophiles to afford the corresponding Diels-Alder cycloadducts in good yields.

Nishida, Goushi’s team published research in Angewandte Chemie, International Edition in 2008 | 139139-86-9

Angewandte Chemie, International Edition published new progress about Alkadiynes Role: RCT (Reactant), RACT (Reactant or Reagent) (1,6-diynes). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Category: chiral-phosphine-ligands.

Nishida, Goushi; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken published the artcile< Enantioselective synthesis of P-stereogenic alkynylphosphine oxides by Rh-catalyzed [2+2+2] cycloaddition>, Category: chiral-phosphine-ligands, the main research area is alkynyl phosphine oxide preparation stereoselective structure; cycloaddition dialkynyl phosphine oxide diyne rhodium binap complex catalyst; crystal mol structure stereogenic phosphorus alkynyl phosphine oxide preparation.

An enantioselective synthesis of P-stereogenic alkynylphosphine oxides through a cationic rhodium(l)/modified-binap complex catalyzed [2+2+2] cycloaddition of sym. dialkynylphosphine oxides with 1,6-diynes was developed (binap = 2,2′-bis(diphenylphosphinyl)-1,1′-binaphthyl, Z = CH2, O, or N-sulfonamide). Furthermore, this method permits the synthesis of a C2-sym. P-stereogenic bis(alkynylphosphine oxide). A crystal structure of one product was determined along with the absolute configuration of the phosphorus center.

Oonishi, Yoshihiro’s team published research in Angewandte Chemie, International Edition in 2019 | 139139-86-9

Angewandte Chemie, International Editionpublished new progress about Alcohols, unsaturated 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, Recommanded Product: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl.

Oonishi, Yoshihiro; Masusaki, Shuichi; Sakamoto, Shunki; Sato, Yoshihiro published the artcile< Rhodium(I)-Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh-C Bond by a Tethered Hydroxy Group>, Recommanded Product: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is acyl heterocyclic compound enantioselective preparation; enynol preparation enantioselective cyclization rhodium catalyst; cyclization; enantioselectivity; enyne; rhodium; σ-bond metathesis.

Rhodium(I)-catalyzed enantioselective intramol. cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh-C(sp2) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ-bond metathesis of a tethered O-H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alc. moiety were used in this reaction.

Oonishi, Yoshihiro’s team published research in Advanced Synthesis & Catalysis in 2016 | 139139-93-8

Advanced Synthesis & Catalysispublished 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, Synthetic Route of 139139-93-8.

Oonishi, Yoshihiro; Hato, Yoshio; Sato, Yoshihiro published the artcile< Rhodium(I)-Catalyzed Diastereoselective Cycloisomerization of Enynes with Tethered (S)-2-Methyl-2-propanesulfinyl Imine>, Synthetic Route of 139139-93-8, 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.

Masutomi, Koji’s team published research in Angewandte Chemie, International Edition in 2012 | 139139-86-9

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

Masutomi, Koji; Sakiyama, Norifumi; Noguchi, Keiichi; Tanaka, Ken published the artcile< Rhodium-Catalyzed Regio-, Diastereo-, and Enantioselective [2+2+2] Cycloaddition of 1,6-Enynes with Acrylamides>, Synthetic Route of 139139-86-9, the main research area is enyne enantioselective diastereoselective regioselective cycloaddition acrylamide rhodium BINAP catalyst; isoindole indene isobenzofuran amide hexahydro enantioselective diastereoselective synthesis.

A variety of partially hydrogenated isoindoles I [X = NTs; R1 = H, Me, Ph; R2 = H, Me, Et, Ph; R3 = R4 = Me, n-Bu, Ph; R3 = Me, R4 = MeO, Ph; R3R4 = (CH2)4] and their carbocyclic I [X = (MeO2C)2C; R1 = R2 = R3 = Me; R4 = Ph] and oxacyclic analogs I (X = O; R1 = n-pentyl; R2 = R3 = Me; R4 = Ph) was synthesized by rhodium(I)/(R)-H8-BINAP-catalyzed asym. [2 + 2 + 2] cycloaddition of 1,6-enynes II with acrylamides H2C:CHC(O)NR3R4. In this catalysis, regioselective insertion of acrylamide into a rhodacyclopentene intermediate and the coordination of the carbonyl group of acrylamide to the cationic rhodium center suppress the undesired β-hydride elimination.

Shintani, Ryo’s team published research in Journal of the American Chemical Society in 2006-05-03 | 139139-86-9

Journal of the American Chemical Societypublished new progress about Boronic acids Role: RCT (Reactant), RACT (Reactant or Reagent) (arylboronic acids). 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Electric Literature of 139139-86-9.

Shintani, Ryo; Duan, Wei-Liang; Hayashi, Tamio published the artcile< Rhodium-Catalyzed Asymmetric Construction of Quaternary Carbon Stereocenters: Ligand-Dependent Regiocontrol in the 1,4-Addition to Substituted Maleimides>, Electric Literature of 139139-86-9, the main research area is rhodium complex asym addition reaction regioselectivity enantioselectivity; arylboronic acid maleimide asym addition reaction.

A rhodium-catalyzed asym. 1,4-addition of arylboronic acids of formula ArB(OH)2 (Ar = Ph, 2-naphthyl, 2-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl) to substituted maleimides (I; R = Et, Me, i-Pr) has been described. The regioselectivity in this reaction is controlled by the choice of ligand (dienes or bisphosphines), and 1,4-adducts with a quaternary stereocenter (II; Ar, R = same as above) can be obtained with high regio- and enantioselectivity over 1,4-adducts with a secondary carbon center (III; Ar, R = same as above) by the use of (R)-H8-BINAP (IV). For example, I (R = Et), 3.0 equiv phenylboronic acid, 2.5 mol% divinylrhodium chloride dimer, IV (Rh/ligand = 1:1), and 0.5 equiv KOH were stirred in a 10:1 mixture of dioxane and water at 50° for 3 h to give a 87:13 mixture of II (Ar = Ph, R = Et) and III (Ar = Ph, R = Et) in 98% yield.

Yang, Bo’s team published research in Angewandte Chemie, International Edition in 2020-11-23 | 139139-86-9

Angewandte Chemie, International Editionpublished new progress about Crystal structure. 139139-86-9 belongs to class chiral-phosphine-ligands, and the molecular formula is C44H40P2, Formula: C44H40P2.

Yang, Bo; Yang, Wu; Guo, Yonghong; You, Lijun; He, Chuan published the artcile< Enantioselective Silylation of Aliphatic C-H Bonds for the Synthesis of Silicon-Stereogenic Dihydrobenzosiloles>, Formula: C44H40P2, the main research area is rhodium catalyzed enantioselective silylation cyclization styrene derivative arylsilane; silicon stereogenic dihydrobenzosilole containing dehydrocholesterol preparation crystal structure; mol structure silicon stereogenic dihydrobenzosilole containing dehydrocholesterol; C(sp3)−H silylation; asymmetric catalysis; dihydrobenzosiloles; hydrosilylation; silanes.

A Rh(I)-catalyzed enantioselective silylation of aliphatic C-H bonds for the synthesis of Si-stereogenic dihydrobenzosiloles is demonstrated. This reaction involves a highly enantioselective intramol. C(sp3)-H silylation of dihydrosilanes, followed by a stereospecific intermol. alkene hydrosilylation leading to the asym. tetrasubstituted silanes. A wide range of dihydrosilanes and alkenes displaying various functional groups are compatible with this process, giving access to a variety of highly functionalized Si-stereogenic dihydrobenzosiloles in good to excellent yields and enantioselectivities.

Sagae, Hiromi’s team published research in Chemical Communications (Cambridge, United Kingdom) in 2008-08-28 | 139139-86-9

Chemical Communications (Cambridge, United Kingdom)published new progress about Alkenynes Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation) (dienynes). 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.

Sagae, Hiromi; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken published the artcile< Rhodium-catalyzed enantio- and diastereoselective intramolecular [2 + 2 + 2] cycloaddition of unsymmetrical dienynes>, Recommanded Product: (R)-2,2′-Bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl, the main research area is dienyne rhodium catalyst intramol cycloaddition; polycyclic cyclohexene derivative stereoselective preparation crystal structure; benzopyran derivative stereoselective preparation; biscyclooctadienerhodium tetrafluoroborate octahydrobinap asym cycloaddition catalyst.

A cationic rhodium(I)/(R)-H8-BINAP or (R)-Segphos complex catalyzes an intramol. [2 + 2 + 2] cycloaddition of unsym. dienynes, leading to fused tri- and tetracyclic cyclohexenes bearing two tertiary or quaternary carbon centers in high yields with high enantio- and diastereoselectivity.

Bandini, Marco’s team published research in Journal of Organometallic Chemistry in 2010 | 325168-88-5

Journal of Organometallic Chemistrypublished new progress about Allylic alcohols Role: RCT (Reactant), SPN (Synthetic Preparation), RACT (Reactant or Reagent), PREP (Preparation). 325168-88-5 belongs to class chiral-phosphine-ligands, and the molecular formula is C48H50P2, Recommanded Product: (S)-(+)-4,12-Bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane.

Bandini, Marco; Gualandi, Andrea; Monari, Magda; Romaniello, Alessandro; Savoia, Diego; Tragni, Michele published the artcile< Allylic alcohols: Valuable synthetic equivalents of non-activated alkenes in gold-catalyzed enantioselective alkylation of indoles>, Recommanded Product: (S)-(+)-4,12-Bis(di(3,5-xylyl)phosphino)-[2.2]-paracyclophane, the main research area is allylic alc tethered indole derivative preparation; chiral ligand gold catalyzed intramol allylic alkylation indole derivative; tetrahydrocarbazole derivative stereoselective preparation; tetrahydrocarboline derivative stereoselective preparation.

The recent booming of gold catalysis has demonstrated that unprecedented transformations can be realized in a highly selective manner. Moreover, due to the growing availability of chiral organic ligands, gold-catalysis can be considered as one of most dynamic hot spots in asym. synthesis. However, in this context, the use of non-activated olefinic C-C double bonds is still largely unexplored due to the intrinsic inertness of C=C (respect to allenes and alkynes) in taking part in nucleophilic additions assisted by π-electrophilic activations. Allylic alcs. have been demonstrated to be feasible “”surrogates”” of non-activated alkenes for the enantioselective allylic alkylation of indoles catalyzed by chiral gold(I) complexes. In this investigation, a full account addressing efficiency and substrate scope of such a process is presented. The products, tetrahydrocarbazoles or tetrahydro-β-carbolines, are obtained in moderate to good yields and 40-86% ee from the corresponding Z-allylic alc.-containing substrates, while the E isomers are unreactive.