Figure 73: The proposed catalyst/substrate interaction shown in Figure 73 corresponds to the related sulfoxidation catalyzed by chiral phosphoric acid PA 5 (ref 133). Please note that this interaction will be different for PA 43. Figure 105 and surrounding text: The asymmetric reduction was achieved with 1 mol % (S)-PA 25 (ref ). Figure 176 and surrounding text: For the first example of the application of asymmetric counteranion directed catalysis with phosphoric acid salts as catalysts, see ref 29d. Figure 192: The proposed transition state corresponds to the spiroacetalization catalyzed by chiral phosphoric acid (S)-PA 25 (ref 373). Please note that this will be different for PA 43. Figure 196: The correct substrate used is TMSN3. Please note that an alternative mechanism has been proposed (ref 381), as discussed in the surrounding text. Figure 228: The correct structure of 427 is

Addition and Correction to Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates

The first enantioselective Friedel–Crafts alkylation of indoles and pyrroles with 3-hydroxy-3-indolyloxindoles to access two novel types of 3,3-diaryloxindoles catalyzed by chiral imidodiphosphoric acids has been reported. A range of quaternary carbon centered 3,3-diaryloxindoles were synthesized in high yield (up to >99%) with excellent enantioselectivity (up to 98% ee) at low catalyst loadings (as low as 0.5 mol%). The Friedel–Crafts reaction between indoles and 3-hydroxy-3-indolyloxindoles is amenable to gram scale syntheses.

Chiral Imidodiphosphoric Acids-Catalyzed Friedel–Crafts Reactions of Indoles/Pyrroles with 3-Hydroxy-indolyloxindoles: Enantioselective Synthesis of 3,3-Diaryloxindoles

Organocatalyzed nucleophilic addition of pyrazoles to 2H-azirines: asymmetric synthesis of 3,3-disubstituted aziridines and kinetic resolution of racemic 2H-azirines

This review aims to bring light upon a very interesting group of compounds, the 1,4-dihydropyridines (1,4-DHPs). These structures are well-known pharmacophores, used for many years to treat cardiovascular diseases because of their activity as calcium channel blockers. In addition, their potential as drugs to treat other affections has been recently exposed. The racemic synthesis of 1,4-DHPs has been well studied, while the asymmetric approaches are mainly based on the use of chiral auxiliaries or chiral resolutions. However, there are scarce examples regarding enantioselective organocatalytic methods. Herein, we will summarize the existing examples in this field of research.

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Organocatalytic Enantioselective Synthesis of 1,4-Dihydropyridines

Thiohydantoins: synthetic strategies and chemical reactions

Penta-substituted 1,4-dihydropyridines were synthesized via catalytic enantioselective cyclization reactions of β,γ-unsaturated α-ketoesters, arylamines and acetylacetone for the first time. H 8 -BINOL-type chiral imidodiphosphoric acid 4c was a suitable catalyst and exhibited high catalytic and stereocontrolling abilities in these enone-type reactions. Under the optimized conditions, these 1,4-dihydropyridines were obtained with excellent enantioselectivities (up to 97% ee). In addition, the typical product 8ba was converted into the corresponding substituted piperidine with high yield (87%) and excellent enantioselectivity (95% ee) in a single-step reduction.

H8-BINOL chiral imidodiphosphoric acids catalyzed cyclization reactions of β,γ-unsaturated α-ketoesters, arylamines and 1,3-dicarbonyl compounds: enantioselective synthesis of 1,4-dihydropyridines

Different N–C–N formation reactions of aromatic aldehydes and thiohydantoins controlled by Lewis acid promoters

The invention discloses a method utilizing a micro-reactor to continuously synthesize amide herbicide, and belongs to the technical field of organic synthesis. The method takes substituted aniline as the raw material, and then the substituted aniline is subjected to continuous two steps of N-acylation and heterogeneous N-alkylation in a micro-reactor so as to obtain the amide herbicide; wherein the conversion rate of substituted aniline can reach 98% or more, the total yield of the reactions can exceed 95%, and the product purity is more than 96%. The intermediate purifying step is saved, thus the production procedure is simplified, the reaction time is reduced, the alkali solution consumption is reduced, the production equipment is simple, the production efficiency is high, and the product yield and purity are high.

Method utilizing micro-reactor to continuously synthesize amide herbicide

The invention relates to a method for preparing plerixafor and belongs to the technical field of pharmaceutical synthesis The method comprises the following steps: firstly performing coupling reaction on 1, 4, 8, 11-tetraaza-5, 7, 12-trioxocyclotetradecane and terephthaloyl chloride, and then reducing and purifying an obtained intermediate, namely terephthaloyl-substituted bis (1, 4, 8, 11-tetraaza-5, 7, 12-trioxocyclotetradecane) to obtain a target product, namely plerixafor The coupling reaction can be performed in a conventional flask and other reactors and can also be performed in a microreactor As terephthaloyl chloride has relatively high activity, the reaction yield with 1, 4, 8, 11-tetraaza-5, 7, 12-trioxocyclotetradecane can achieve 992% and the total yield of plerixafor can achieve 818% The method has the characteristics of simple process and equipment, high production efficiency, high product yield, easiness in enlargement and the like and is a green, environmentally friendly and efficient method for synthesizing plerixafor

Method for preparing plerixafor

H8‐BINOL Chiral Imidodiphosphoric Acids Catalyzed Cyclization Reactions of β,γ‐Unsaturated α‐Ketoesters, Arylamines and 1,3‐Dicarbonyl Compounds: Enantioselective Synthesis of 1,4‐Dihydropyridines.

Guangliang Zhang

Papers

H8-BINOL chiral imidodiphosphoric acids catalyzed cyclization reactions of β,γ-unsaturated α-ketoesters, arylamines and 1,3-dicarbonyl compounds: enantioselective synthesis of 1,4-dihydropyridines

Different N–C–N formation reactions of aromatic aldehydes and thiohydantoins controlled by Lewis acid promoters

Method utilizing micro-reactor to continuously synthesize amide herbicide

Method for preparing plerixafor

H8‐BINOL Chiral Imidodiphosphoric Acids Catalyzed Cyclization Reactions of β,γ‐Unsaturated α‐Ketoesters, Arylamines and 1,3‐Dicarbonyl Compounds: Enantioselective Synthesis of 1,4‐Dihydropyridines.