Mechanistic Dichotomy in the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by Chiral Pyridine <i>N</i>‐Oxides

Malkov, Andrei V.; Stončius, Sigitas; Bell, Mark; Castelluzzo, Fabiomassimo; Ramírez‐López, Pedro; Biedermannová, Lada; Langer, Vratislav; Rulı́s̆ek, Lubomı́r; Kočovský, Pavel

doi:10.1002/chem.201203817

Cited by 38 publications

(18 citation statements)

References 197 publications

(71 reference statements)

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“…1-(2-(2,6-Dimethoxyphenyl)-2-oxoethyl)pyridinium iodide (b) According to as lightly modified literature procedure, 1-(2,6-dimethoxyphenyl)ethanone (20 mmol) and iodine (24 mmol) were heated to reflux for 3hin pyridine (50 mL). [21] The reaction mixture was cooled to 0 8Ca nd the yellow product was precipitated, filtered, and washed with cold pyridine (yield 88 %). Synthesis of 1-(2-Oxo-2-phenylethyl)pyridin-1-iumiodide (c)…”

Section: Experimental Section General Synthetic Procedures For Tetracamentioning

confidence: 99%

Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

et al. 2015

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Tetracarbonyl complexes of low‐valent Group VI transition metals (Mo and W), containing diimine bidentate ligands, namely W(CO)4(4,6‐diphenyl‐2,2′‐bipyridine) (1), W(CO)4(6‐(2,6‐dimethoxyphenyl)‐4‐phenyl‐2,2′‐bipyridine) (2), Mo(CO)4(2,2′‐dipyridylamine) (3), and W(CO)4(2,2′‐dipyridylamine) (4), were synthesized and tested as homogeneous catalysts for the electrochemical reduction of CO2 in nonaqueous media. Cyclic voltammetry performed under a CO2 atmosphere, revealed that these complexes have significant catalytic activity in acetonitrile, and gas chromatographic measurements together with exhaustive electrolysis showed that CO is the major reduction product. Mechanistic insights were obtained by IR‐spectroelectrochemical measurements. The substantially different electrocatalytic performances obtained for the two classes of catalysts are compared and discussed.

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Section: Experimental Section General Synthetic Procedures For Tetracamentioning

confidence: 99%

Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

et al. 2015

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“…This explains why allylation is the most popular testing reaction and is very well examined. It has also become a standard testing ground for new chiral Lewis basic organocatalysts [5][6][7]11]. The good selectivity is obtained when the catalyst allows the reaction to proceed via a closed cyclic chair-like transition state involving hypervalent silicates, as shown in Scheme 1.…”

Section: Chiral Heteroaromatic N-oxides As Organocatalystsmentioning

confidence: 99%

Heteroaromatic N-Oxides in Asymmetric Catalysis: A Review

Wrzeszcz

Siedlecka

2020

Molecules

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An increasing interest in the synthesis and use of optically active pyridine N-oxides as chiral controllers for asymmetric reactions has been observed in the last few years. Chiral heteroaromatic N-oxides can work as powerful electron-pair donors, providing suitable electronic environments in the transition state formed within the reaction. The nucleophilicity of the oxygen atom in N-oxides, coupled with a high affinity of silicon to oxygen, represent ideal properties for the development of synthetic methodology based on nucleophilic activation of organosilicon reagents. The application of chiral N-oxides as efficient organocatalysts in allylation, propargylation, allenylation, and ring-opening of meso-epoxides, as well as chiral ligands for metal complexes catalyzing Michael addition or nitroaldol reaction, can also be found in the literature. This review deals with stereoselective applications of N-oxides, and how the differentiating properties are correlated with their structure. It contains more recent results, covering approximately the last ten years. All the reported examples have been divided into five classes, according to the chirality elements present in their basic molecular frameworks.

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“…Recent advances in asymmetric catalysis resulted in utilizing the less discussed electrophilic properties of iminium type intermediates in complex annulations of indoles [285,286] and also pyridines [287,288]. Shibatomi and Narayama discussed the catalytic enantioselective -chlorination of carbonyl compounds and stereospecific substitution reactions of the resulting optically active alkyl chlorides [289].…”

Section: Journal Of Catalystsmentioning

confidence: 99%

Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View

Shaikh

2014

Journal of Catalysts

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This paper purports to review catalysis, particularly the organocatalysis and its origin, key trends, challenges, examples, scope, and importance. The definition of organocatalyst corresponds to a low molecular weight organic molecule which in stoichiometric amounts catalyzes a chemical reaction. In this review, the use of the termheterogenized organocatalystwill be exclusively confined to a catalytic system containing an organic molecule immobilized onto some sort of support material and is responsible for accelerating a chemical reaction. Firstly, a brief description of the field is provided putting it in a green and sustainable perspective of chemistry. Next, research findings on the use of organocatalysts on various inorganic supports including nano(porous)materials, nanoparticles, silica, and zeolite/zeolitic materials are scrutinized in brief. Then future scope, research directions, and academic and industrial applications will be outlined. A succinct account will summarize some of the research and developments in the field. This review tries to bring many outstanding researches together and shows the vitality of the organocatalysis through several aspects.

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Mechanistic Dichotomy in the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by Chiral Pyridine N‐Oxides

Cited by 38 publications

References 197 publications

Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

Heteroaromatic N-Oxides in Asymmetric Catalysis: A Review

Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View

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Mechanistic Dichotomy in the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by Chiral Pyridine N‐Oxides

Cited by 38 publications

References 197 publications

Electrochemical Reduction of CO2 by M(CO)4(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

Electrochemical Reduction of CO2 by M(CO)4(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

Heteroaromatic N-Oxides in Asymmetric Catalysis: A Review

Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View

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Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine

Electrochemical Reduction of CO₂ by M(CO)₄(diimine) Complexes (M=Mo, W): Catalytic Activity Improved by 2,2′‐Dipyridylamine