91663-37-5

Upstream product

• 930-68-7 cyclohexenone 
• 16419-60-6 2-Methylphenylboronic acid 
• 91663-36-4 3-(2-methylphenyl)cyclohexanone 
• 95-46-5 2-methylphenyl bromide 
• 6699-93-0 (2-methylphenyl)lithium 
• 932-31-0 ortho-tolylmagnesium bromide 

Relevant academic research and scientific papers

Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones

Chiral N-aryl sulfinamide-olefins which are readily synthesized via C-N coupling and nucleophilic substitution have been used as chiral ligands, which demonstrate moderate to excellent asymmetric catalytic performance in the rhodium-catalyzed asymmetric 1

Fine-Tuning the Bicyclo[3.3.1]nona-2,6-diene Ligands: Second Generation 4,8-Substituted Dienes for Rh-Catalyzed Asymmetric 1,4-Addition Reactions

Design and synthesis of the second generation C2-symmetric 4,8-endo,endo-bis(alkoxy) bicyclo[3.3.1]nona-2,6-diene ligands possessing additional 4,8-exo,exo substituents is reported. The 4,8-exo,exo groups provide a further element for fine-tuning of the ligand structure by enforcing conformational rigidity of the 4,8-endo,endo side chains. Such tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were employed as steering ligands in the rhodium-catalyzed arylation of cyclic enones with arylboronic acids, providing the corresponding 1,4-addition products in good to excellent yields (69–99 %) and enantioselectivities up to 99 % ee.

Asymmetric Baeyer-Villiger oxidation: Classical and parallel kinetic resolution of 3-substituted cyclohexanones and desymmetrization of: Meso -disubstituted cycloketones

Regioselectivity is a crucial issue in Baeyer-Villiger (BV) oxidation. To date, few reports have addressed asymmetric BV oxidation of 3-substituted cycloketones due to the high difficulty of controlling regio- and stereoselectivity. Herein, we report the asymmetric BV oxidation of 3-substituted and meso-disubstituted cycloketones with chiral N,N′-dioxide/Sc(iii) catalysts performed in three ways: classical kinetic resolution, parallel kinetic resolution and desymmetrization. The methodology was applied in the total and formal synthesis of bioactive compounds and natural products. Control experiments and calculations demonstrated that flexible and adjustable catalysts played a significant role in the chiral recognition of substrates.

Heterogeneous Chiral Diene-Rh Complexes for Asymmetric Arylation of α,β-Unsaturated Carbonyl Compounds, Nitroalkenes, and Imines

A chiral diene ligand with tertiary alkyl amine-derived secondary amide moiety was immobilized on cross-linked polystyrene (PS) by radical polymerization, which was combined with Rh to form heterogeneous chiral Rh complexes (PS-diene Rh?Cl). PS-diene Rh?Cl catalyzed asymmetric arylation reactions of α,β-unsaturated carbonyl compounds (ketones, esters, and amides), nitroalkenes, and imines afforded the desired products in high yields with excellent enantioselectivities. PS-diene Rh?Cl is stable in air, can be stored for several months, and can be reused more than 10 times without any reduction of either yield or enantioselectivity. We also developed a method of activation of PS-diene Rh?Cl to generate more active species. (Figure presented.).

Steric Tuning of Sulfinamide/Sulfoxides as Chiral Ligands with C1, Pseudo-meso, and Pseudo-C2 Symmetries: Application in Rhodium(I)-Mediated Arylation

A new family of sulfinamide/sulfoxide derivatives was synthesized as chiral bidentate ligands by stereoselective additions of methylsulfinyl carbanions to N-tert-butylsulfinylimines. The new ligands, with C1, pseudo-meso, and pseudo-C2 symmetries, were successfully assayed in Rh-catalyzed additions of arylboronic acids to activated ketones. The sterically dissymmetric C1 ligand (RS,SC,RS)-N-[1-(phenylsulfinyl)-3-methylbut-2-yl] tert-butylsulfinamide turned out to be the optimal one, allowing the 1,4-additions of diverse arylboronic acids, on different α,β-unsaturated cyclic ketones with high chemical yields and enantioselectivities up to >99% ee.

A novel, C2-symmetric, chiral bis-cyclosulfinamide-olefin tridentate ligand in Rh-catalyzed asymmetric 1,4-additions

A C2-symmetric, chiral bis-cyclosulfinamide-olefin ligand composed of two 1-oxo-2,3-dihydro-1,2-benzisothiazole moieties with rigid skeletons and a conformationally flexible butenylene chain is disclosed for the first time. HRMS and 1/sup

Synthesis of Highly Enantioenriched Propelladienes and their Application as Ligands in Asymmetric Rh-Catalyzed 1,4-Additions

The first synthesis of highly enantioenriched [4.3.3]propelladienes is reported. The novel bridged bicyclo[3.3.0] dienes were applied as steering ligands in the rhodium-catalyzed asymmetric arylation of cyclic enones. The catalytic system showed high catalytic activity, and the 1,4-adducts were obtained in good to excellent yields (46-99%) with enantioselectivities up to 96% ee.

Dicyclic sulfamide-alkene chiral ligand as well as preparation method and application

The invention discloses a dicyclic sulfamide-alkene chiral ligand as well as a preparation method and application. The structural characteristic of the dicyclic sulfamide-alkene chiral ligand is thatthe chiral ligand is a C2 symmetric compound formed by c

A diastereomeric pair of sulfoxide-containing chiral MOP-type ligands: Preparation and application to rhodium-catalyzed asymmetric 1,4-addition reactions

(R,SS)-Sulfoxide-MOP (L2) and (R,RS)-sulfoxide-MOP (L3) were developed as a diastereomeric pair of sulfoxide-containing chiral MOP-type ligands. These two ligands also represent the first monosulfoxide analogues of BINAP. The chiral ligand L2 was successfully applied to the highly enantioselective rhodium-catalyzed 1,4-addition between α,β-unsaturated ketones or esters and arylboronic acids, and exhibited a broad substrate scope when the reaction was performed using 1.5 mol% Rh in cyclohexane/H2O (10:1) at 40 °C under mild basic conditions.

Chiral Bicyclic Bridgehead Phosphoramidite (Briphos) Ligands for Asymmetric Rhodium-Catalyzed 1,2- and 1,4-Addition

A complementary solution for Rh-catalyzed enantioselective 1,2- and 1,4-arylation with two structurally related chiral ligands is reported. A chiral bicyclic bridgehead phosphoramidite (briphos) ligand derived from 1-aminoindane was efficient for the 1,2-arylation of N-sulfonyl imines, while that derived from 1,2,3,4-tetrahydro-1-naphthylamine was efficient for 1,4-arylation of α,β-unsaturated cyclic ketones. For α,β-unsaturated N-tosyl ketimines, the briphos derived from 1-aminoindane was found to selectively provide γ, γ-diaryl N-tosyl enamines with high yields and stereoselectivities.