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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

Synthesis of Silicon-Stereogenic Silanols Involving Iridium-Catalyzed Enantioselective C-H Silylation Leading to a New Ligand Scaffold

Despite a growing focus on the construction of highly enantioenriched silicon-stereogenic organosilicon compounds, the enantioselective synthesis of silicon-stereogenic silanols through asymmetric catalysis remains a considerable challenge. Herein, we realized enantioselective construction of silicon-stereogenic diarylsilanols via an Ir-catalyzed C-H silylation of diarylsilanols along with stereospecific substitution or Tamao-Fleming oxidation. This strategy gives rise to a class of chiral diol catalyst cores (PSiOLs). Transformation of PSiOLs led to the ligand possessing both Si and P-stereocenters, which is capable of inducing excellent enantioselectivity in the rhodium(I)-catalyzed conjugate 1,4-addition of aryl boronic acids to cyclohexenone.

Tricyclic Sulfoxide-Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The "Matched" Diastereomer Catalyzes Asymmetric C-C Bond Formations

Deprotonation of phenyldibenzo[b,f]tropylidene (8) with LDA/t-BuOK followed by quenching with either diastereomer of inexpensive glucose-based t-Bu-sulfinate (R)- or (S)-11 affords a sulfoxide-alkene hybrid ligand as the diastereomeric pairs (SS,SC)-9/(SS,RC)-10 and (RS,RC)-9/(RS,SC)-10, respectively, which via chromatographic/recrystallization may be separated into the four isomers. The optically pure diastereomeric ligands (SS,SC)-9 and (SS,RC)-10 react with [RhCl(coe)2]2 to form the dinuclear complexes (RS,SC)-11 and (RS,RC)-12, respectively, in which the bidentate ligands coordinate the metal centers through the sulfur and alkene donor functions. These complexes catalyze the conjugate addition of arylboronic acids to cyclic Michael acceptors with enantioselectivities of up to 99% ee. DFT calculations show the preponderant influence of planar chirality of the ligand alkene function. The enantioselectivity switch observed between (RS,SC)-11 and (RS,RC)-12 is explained by the inverted cis-trans coordinations of the substrate molecules in catalytic steps.

A consecutive process for C-C and C-N bond formation with high enantio-and diastereo-control: Direct reductive amination of chiral ketones using hydrogenation catalysts

High diastereoselectivity was observed in the Rh-catalysed reductive amination of 3-arylcyclohexanones to form tertiary amines. This was incorporated into a one-pot enantioselective conjugate addition and diastereoselective reductive amination, including an example of assisted tandem catalysis.

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.

Developing Chiral Dibenzazepine-Based S(O)-Alkene Hybrid Ligands for Rh(I) Complexation: Catalysts for the Base-Free Hayashi-Miyaura Reaction

A stereodivergent synthesis using inexpensive reagents, i.e., dibenzazepine and glucose-derived t-Bu-sulfinate diastereomers (RS)-6 or (SS)-6, affords respective S(O)-alkene hybrid ligands (S)-7 and (R)-7 on gram scales and in excellent optical purity (ee > 99%). Phenyl substitution of the dibenzoazepine backbone generates planar chirality to give epimerization-resistant (pS,RS)-10 diastereoisomer in high isomeric purity. Furthermore, the crystal structure of widely used sulfinate (RS)-6 is disclosed for the first time since its discovery a quarter of a century ago. Ligands 7 and 10 coordinate Rh(I) in a bidentate fashion through the S atoms and the alkene functions as evidenced by the crystal structures of complexes (R)-11 and (SN,SS)-12. (R)-11 catalyzes the conjugate addition of arylboronic acids to enones with enantioselectivities of up to 77% ee. The reaction proceeds smoothly also under base-free conditions at 40 °C. The planar chirality in ligand (pS,RS)-10 is shown to override and invert the sense of chiral induction predicted by the configuration of the sulfur donor atom.

Pd NPs-Loaded Homochiral Covalent Organic Framework for Heterogeneous Asymmetric Catalysis

We herein report the fabrication of a palladium nanoparticles (Pd NPs) loaded homochiral covalent organic framework using S-(+)-2-methylpiperazine and cyanuric chloride (Pd@CCOF-MPC) (2) via a very facile chemical approach. The chiral COF support of 1 (CC

Chiral Phosphorus-Olefin Ligands for the RhI-Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins

New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; t

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.

A New Type of Chiral Cyclic Sulfinamide–Olefin Ligands for Rhodium-Catalyzed Asymmetric Addition

A new type of chiral cyclic sulfinamide–olefin ligands, N-allylic 2,3-dihydro-1,2-benzoisothiazole 1-oxides, with 2,3-dihydro-1,2-benzoisothiazole 1-oxide as a unique chiral skeleton, is developed for the highly enantioselective rhodium-catalyzed asymmetr