Day: December 30, 2022

Asymmetric construction of polycyclic indoles through olefin cross-metathesis/intramolecular Friedel-Crafts alkylation under sequential catalysis was written by Cai, Quan;Zhao, Zhuo-An;You, Shu-Li. And the article was included in Angewandte Chemie, International Edition in 2009.Synthetic Route of C48H29O4P This article mentions the following:

Sequential catalytic olefin cross-metathesis of allyloxymethyl and allylaminomethyl indoles and enones followed by enantioselective Friedel-Crafts alkylation produced polycyclic indoles containing the tetrahydropyranoindole and tetrahydro-β-carboline ring systems, such as I and II, in excellent yields and excellent enantioselectivities. Chiral phosphoric acids were used as catalysts for the Friedel-Crafts alkylations of indolyl enones while both a ruthenium complex and chiral phosphoric acids were used as catalysts for sequential olefin cross-metathesis and Friedel-Crafts alkylations of allyloxymethyl or allylaminomethyl indoles and enones. In the experiment, the researchers used many compounds, for example, (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3Synthetic Route of C48H29O4P).

(11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Synthetic Route of C48H29O4P

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

On the asymmetric iridium-catalyzed N-allylation of amino acid esters: Improved selectivities through structural variation of the chiral phosphoramidite ligand was written by Albat, Dominik;Kocher, Alicia;Witt, Julia;Schmalz, Hans-Guenther. And the article was included in European Journal of Organic Chemistry in 2022.SDS of cas: 252288-04-3 This article mentions the following:

The investigation of the iridium-catalyzed asym. N-allylation of tert-Bu glycinate using a “branched” racemic 1-vinyl-alkyl Me carbonate revealed severe limitations of existing protocols. By screening a set of 24 BINOL-derived chiral phosphoramidites a new superior ligand (L24*) was identified which afforded the amination product with high enantioselectivity (≥95% ee) under optimized conditions. This ligand also allowed the N-allylation of other amino acid tert-Bu esters (derived from alanine, phenylalanine, or proline) with outstanding levels of diastereocontrol (d.r. ≥99 : 1) and negligible matched/mismatched differences. In the experiment, the researchers used many compounds, for example, (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3SDS of cas: 252288-04-3).

(11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3) belongs to chiral phosphine ligands. The synthesis of novel trialkylphosphines can be quite difficult, thereby limiting the scope of their chiral variants. Asymmetric catalytic performance is determined not only by the metal center but also by the chiral ligand selected.SDS of cas: 252288-04-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Carbon-Carbon Bond-Forming Enantioselective Synthesis of Chiral Organosilicon Compounds by Rhodium/Chiral Diene-Catalyzed Asymmetric 1,4-Addition Reaction was written by Shintani, Ryo;Okamoto, Kazuhiro;Hayashi, Tamio. And the article was included in Organic Letters in 2005.Reference of 252288-04-3 This article mentions the following:

A new synthetic method for chiral organosilicon compounds through a Rh-catalyzed asym. 1,4-addition of arylboronic acids to β-silyl α,β-unsaturated carbonyl compounds was developed. By employing (R,R)-Bn-bod^* as a ligand, a range of arylboronic acids can be coupled with these substrates in very high enantiomeric excess. The resulting β-silyl 1,4-adducts can be converted to β-hydroxy carbonyl compounds or allylsilanes while retaining their stereochem. information. In the experiment, the researchers used many compounds, for example, (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3Reference of 252288-04-3).

(11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Trivalent phosphorus compounds called phosphines have a tetrahedral electron-group geometry which makes them structurally analogous to amines.Reference of 252288-04-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

C₂-symmetric bicyclo[3.3.1]nonadiene as a chiral ligand for rhodium-catalyzed asymmetric arylation of N-(4-nitrobenzenesulfonyl)arylimines was written by Otomaru, Yusuke;Tokunaga, Norihito;Shintani, Ryo;Hayashi, Tamio. And the article was included in Organic Letters in 2005.Synthetic Route of C24H22NO2P This article mentions the following:

Nonracemic (+)-2,6-diphenylbicyclo[3.3.1]-2,6-nonadiene (I) is prepared in two steps from 2,6-bicyclo[3.3.1]nonanedione; complex {Rh[(+)-I]₂Cl}₂ (II) is an effective catalyst for the addition of arylboroxines [(R)BO]₃ (R = Ph, 4-ClC₆H₄, 4-MeOC₆H₄, 3-MeOC₆H₄, 2-MeC₆H₄) to N-(4-nitrobenzenesulfonyl)imines R¹C(:NNs)H (R¹ = Ph, 4-ClC₆H₄, 4-BrC₆H₄, 4-MeO₂CC₆H₄, 4-MeOC₆H₄, 2-MeC₆H₄, 1-naphthyl, 2-thienyl; Ns = 4-O₂NC₆H₄SO₂) to yield nonracemic diarylmethylamines RCH(NHNs)R¹ in 94-99% yields and in 95-99% ee. Addition of phenyllithium and cerium chloride to 2,6-bicyclo[3.3.1]nonanedione followed by phosphorus oxychloride-mediated elimination yields racemic I which is resolved by chiral HPLC to yield (+)-I; reaction of (+)-I with [Rh(C₂H₄)₂Cl]₂ yields II. Catalysts generated in situ from bisphosphines and [Rh(C₂H₄)₂Cl]₂ are ineffective for the enantioselective addition reaction; catalysts generated from either a binaphthyldiol phosphoramidite or nonracemic bicyclic dienes and [Rh(C₂H₄)₂Cl]₂ catalyze the enantioselective addition but with lower enantioselectivities than II. Deprotection of the 4-nitrobenzenesulfonyl group with benzenethiol and potassium carbonate in DMF yields the free diarylmethylamines in two cases with no loss of enantioselectivity. In the experiment, the researchers used many compounds, for example, (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3Synthetic Route of C24H22NO2P).

(11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3) belongs to chiral phosphine ligands. Although many reactions require more nucleophilic trialkylphosphines as catalysts, only a few chiral trialkylphosphines are available. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Synthetic Route of C24H22NO2P

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Organocatalytic Enantioselective 1,10-Addition of Alkynyl Indole Imine Methides with Thiazolones: An Access to Axially Chiral Tetrasubstituted Allenes was written by Lin, Xiao;Shen, Boming;Wang, Ziyang;Cheng, Yuyu;Chen, Xuling;Li, Pengfei;Yu, Peiyuan;Li, Wenjun. And the article was included in Organic Letters in 2022.Recommanded Product: (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide This article mentions the following:

An asym. organocatalytic remote 1,10-addition of alkynyl indole imine methides generated in situ from α-(6-indolyl) propargylic alcs. with thiazolones was developed for the first time, affording axially chiral tetrasubstituted allenes featuring vicinal sulfur-containing quaternary carbon stereocenters in high yields with excellent stereoselectivities. The representative scale-up reaction and transformations of the 1,10-adduct were examined The reaction mechanism was expounded by control experiments and DFT calculations In the experiment, the researchers used many compounds, for example, (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3Recommanded Product: (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide).

(11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Recommanded Product: (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Enantioselective Intramolecular Aza-Michael Additions of Indoles Catalyzed by Chiral Phosphoric Acids was written by Cai, Quan;Zheng, Chao;You, Shu-Li. And the article was included in Angewandte Chemie, International Edition in 2010.Application of 1043567-32-3 This article mentions the following:

An asym. intramol. aza-Michael addition of indoles catalyzed by chiral phosphoric acids is described. Enantioenriched tetrahydropyridoindoles, e.g. I (X = CH₂, R = Cl, Me, MeO; X = NBoc, R = H), were obtained in high yields (72-98%) and enantioselectivities (69-93% ee). Sequential olefin cross-metathesis/intramol. aza-Michael addition of indolyl olefins with enones also gave the desired tetrahydropyridoindoles in excellent yields (80-96%) and enantioselectivities (88-93% ee). In the experiment, the researchers used many compounds, for example, (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3Application of 1043567-32-3).

(11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3) belongs to chiral phosphine ligands. Thousands of arylphosphines have been used as chiral ligands for metal-catalyzed asymmetric reactions. Effective chiral catalysts for nucleophilic phosphine catalysis are scarce, seriously limiting the development of asymmetric variants. Application of 1043567-32-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Direct visual detection of the stereoselectivity of a catalytic reaction was written by Eelkema, Rienk;van Delden, Richard A.;Feringa, Ben L.. And the article was included in Angewandte Chemie, International Edition in 2004.Reference of 252288-04-3 This article mentions the following:

Color vision: the enantiomeric excess of the products of an enantioselective catalytic reaction can be determined by a liquid-crystal-based color test. After a simple workup, doping of the reaction product into a liquid crystal affords brightly colored LC phases, with colors depending on the enantiomeric excess of the product. In the experiment, the researchers used many compounds, for example, (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3Reference of 252288-04-3).

(11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3) belongs to chiral phosphine ligands. Generally, the efficiency of nucleophilic phosphine catalysis often depends on the nature of the tertiary phosphine. Chiral ligands coordinate to metal centers to create an asymmetric environment around the reaction centers, which eventually affects enantioselectivity and reaction rate.Reference of 252288-04-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Asymmetric Organocatalytic Synthesis of Bisindoles – Scope and Derivatizations was written by Retich, Christina;Braese, Stefan. And the article was included in European Journal of Organic Chemistry in 2018.SDS of cas: 1043567-32-3 This article mentions the following:

Starting from 3-vinylindoles and glyoxylate imines, the authors created a library of diverse 4,6-bis(1H-indole-3-yl)piperidine 2-carboxylates by using 10 mol-% of a chiral phosphoric acid. Using electron-withdrawing groups on the starting material during the reaction gave Povarov-type structures, which extended the previous library of mols. Furthermore, the authors could demonstrate that consecutive reactions like reductions, cross coupling reactions or click reactions on bisindoles are feasible. In the experiment, the researchers used many compounds, for example, (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3SDS of cas: 1043567-32-3).

(11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3) belongs to chiral phosphine ligands. Thousands of arylphosphines have been used as chiral ligands for metal-catalyzed asymmetric reactions. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. SDS of cas: 1043567-32-3

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Influence of copper salts, solvents, and ligands on the structures of precatalytic phosphoramidite copper complexes for conjugate addition reactions was written by Zhang, Hongxia;Gschwind, Ruth M.. And the article was included in Chemistry – A European Journal in 2007.Name: (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine This article mentions the following:

For Cu-catalyzed enantioselective conjugate addition reactions of organozinc reagents, the available knowledge about the mechanism and the structures involved is still insufficient to understand in detail the strong influences of solvent, salt, and ligand size, or to enable a rational control of this reaction. Screening with three phosphoramidite ligands and four Cu(I) salts using NMR spectroscopy revealed a binuclear Cu complex with mixed trigonal/tetrahedral stereochem. as the basic structural motif of the ground state of precatalysts with highly stereoselective ligands. Ligands with smaller amine moieties allow higher coordination numbers and higher aggregation levels, leading to reduced ee values. Since the ESI mass spectra of several precatalytic Cu halide complexes show a striking correlation with the structures observed in solution, ESI-MS may be used as a fast tool to determine the maximum number of phosphoramidite ligands attached to Cu. In the experiment, the researchers used many compounds, for example, (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3Name: (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine).

(11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine (cas: 252288-04-3) belongs to chiral phosphine ligands. Many phosphine-catalyzed reactions have been developed for the syntheses of various biologically important acyclic and cyclic molecules. Asymmetric variants of these reactions have evolved relatively slowly. Chiral phosphine catalysts: Nucleophilic phosphine catalysis often involves the formation of Lewis adducts, namely phosphonium (di)enolate zwitterions, as reaction intermediates.Name: (11bS)-N,N-Diethyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-amine

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Chiral phosphoric acid-catalyzed asymmetric cascade reaction of C(3) substituted indoles and methyl vinyl ketone was written by Duan, Dehe;Yin, Qin;Wang, Shouguo;Gu, Qing;You, Shuli. And the article was included in Huaxue Xuebao in 2014.Application In Synthesis of (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide This article mentions the following:

Fused indolines bearing a chiral quaternary carbon center at the C(3) position represented very important moieties widely existed in natural products and biol. active compounds Various approaches to access these important scaffolds had been developed. Among them, asym. dearomatizationcyclization cascade reaction was the most concise and effective method by using indole derivatives as starting material. However, the documented reports mainly employed tryptamine or tryptophol derivatives, providing indoline products, such as pyrroloindolines or furoindolines. Therefore, the development of other type of indole derivatives allowing structural diversity was highly desirable. In this paper, an efficient asym. Michael additioncyclization cascade reaction of indole derivatives with Me vinyl ketone (MVK) was developed. After screening various phosphoric acids in the reaction of indole derivative (1a) with MVK, this cascade reaction delivered the dearomative product (2a) in 77% yield and 95% enantiomeric excess in the presence of (R)-SPINOL-derived chiral phosphoric acid (R)-4c with 5Å mol. sieves as additive in CHCl₃ at room temperature Under the optimized reaction conditions, a wide range of substituted indole derivatives bearing both electron-donating and electron-withdrawing groups had been tested. In all cases, the cascade dearomatization reaction proceeded smoothly to afford their corresponding indolo[2,3-b]quinoline products in moderate to good yields and excellent enantioselectivity. The absolute configuration of the products was then determined as (5aR,10bR) by an X-ray crystallog. anal. of a single crystal of enantiopure 2. Moreover, this catalytic system was also feasible in a gram-scale reaction without erosion of enantiomeric excess. And 1.25 g of product 2a could be prepared under the identical conditions in 91% yield and 93% ee. In the experiment, the researchers used many compounds, for example, (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3Application In Synthesis of (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide).

(11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide (cas: 1043567-32-3) belongs to chiral phosphine ligands. Phosphine-catalyzed asymmetric reactions are now powerful and versatile tools for the construction of C–C, C–N, C–O, and C–S bonds and for the syntheses of functionalized carbocycles and heterocycles. Most of these phosphines are acyclic, usually possess low nucleophilic activity, and generally display poor enantioselectivities for phosphine organocatalysis. Application In Synthesis of (11bS)-4-Hydroxy-2,6-di(phenanthren-9-yl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis