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A library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting group to Boc, the enamine was subjected to stereospecific dihydroxylation with OsO4/NMO, resulting in the (1R,2R,3R,5R)-aminodiol diastereomer. The obtained primary aminodiol was transformed to a secondary analogue. The ring closure of the N-benzyl-substituted aminodiol with formaldehyde was investigated and regioselective formation of the spiro-oxazolidine ring was observed. Hydroboration or dihydroxylation of sabinol or its benzyl ether with OsO4/NMO resulted in the formation of sabinane-based diols and triols following a highly stereospecific reaction. Treatment of sabinol with m-CPBA afforded O-benzoyl triol as a diastereoisomer of the directly dihydroxylated product, instead of the expected epoxy alcohol. The resulting aminodiols, diol, and triols were applied as chiral catalysts in the reaction of diethylzinc and benzaldehyde from moderate to good selectivity.

This chapter contains sections titled: Introduction Designing P‐chiral ligands using alcohols as chiral auxiliaries Designing P‐chiral ligands using amino alcohols as chiral auxiliaries Designing of P‐chiral ligands using amines as chiral auxiliaries Conclusion Experimental procedures References

Chiral molecules are stereoselective with regard to specific biological functions. Enantiomers differ considerably in their physiological reactions with the human body. Safeguarding the quality and safety of drugs requires an efficient analytical platform by which to selectively probe chiral compounds to ensure the extraction of single enantiomers. Asymmetric synthesis is a mature approach to the production of single enantiomers; however, it is poorly suited to mass production and allows for only specific enantioselective reactions. Furthermore, it is too expensive and time-consuming for the evaluation of therapeutic drugs in the early stages of development. These limitations have prompted the development of surface-modified nanoparticles using amino acids, chiral organic ligands, or functional groups as chiral selectors applicable to a racemic mixture of chiral molecules. The fact that these combinations can be optimized in terms of sensitivity, specificity, and enantioselectivity makes them ideal for enantiomeric recognition and separation. In chiral resolution, molecules bond selectively to particle surfaces according to homochiral interactions, whereupon an enantiopure compound is extracted from the solution through a simple filtration process. In this review article, we discuss the fabrication of chiral nanoparticles and look at the ways their distinctive surface properties have been adopted in enantiomeric recognition and separation.

Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, the triple bond of alkynes cannot be prochiral. In addition, the linear coordination displayed by gold(I) complexes places the chiral ligand far away from the substrate resulting in an inefficient transfer of chiral information. This poses a significant challenge for the achievement of high enantiocontrol in gold(I)‐catalyzed reactions of alkynes. Although considerable progress on enantioselective gold(I)‐catalyzed transformations has recently been achieved, the asymmetric activation of non‐prochiral alkyne‐containing small molecules still represents a great challenge. Herein we summarize recent advances in intra‐ and intermolecular enantioselective gold(I)‐catalyzed reactions involving alkynes, discussing new chiral ligand designs that lie at the basis of these developments. We also focus on the mode of action of these catalysts, their possible limitations towards a next‐generation of more efficient ligand designs. Finally, square planar chiral gold(III) complexes, which offer an alternative to chiral gold(I) complexes, are also discussed. Striking gold! Several asymmetric gold(I)‐catalyzed transformations have been discovered the last few years. Despite this major progress, the development of enantioselective reactions involving alkynes is still challenging. This minireview summarizes the most recent advances in new‐generation chiral ligand designs, focused on their mode of enantioinduction and limitations. Alternative chiral gold(III)‐catalyzed methodologies are also discussed.

Although many chiral ligands for asymmetric catalysis have been developed, there is still a need for new structures allowing the modular approach. Recently, easy synthesis of chiral pyridine-containing β-amino alcohols has been elaborated by opening respective epoxides with enantiomeric 1-phenylethylamine. This paper reports the synthetic transformation of β-amino alcohols into the new complexing pyridine-containing seleno- and thioethers. The amino alcohols were effectively converted to cyclic sulfonamidates, which were reacted with thiolates or phenyl selenide nucleophile. The reaction was diastereoselective, and its outcome depended on the configuration at the substitution center. The problem was discussed considering DFT optimized structures of both diastereomeric sulfonamidates. New amino-aldimine ligands were also synthesized from chiral pyridine-containing diamines. Nine new chiral ligands were tested in the Tsuji-Trost allylic alkylation resulting in the enantiomerically enriched product in up to 75% ee. The observed stereochemical induction agrees with the prevailing nucleophilic attack at the allylic carbon laying opposite to the complexing nitrogen of pyridine in η3-allylic intermediate complexes.

Salen ligands are a class of Schiff bases simply obtained through condensation of two molecules of a hydroxyl-substituted aryl aldehyde with an achiral or chiral diamine. The prototype salen, or N,N′-bis(salicylidene)ethylenediamine has a long history, as it was first reported in 1889, and immediately, some of its metal complexes were also described. Now, the salen ligands are a class of N,N,O,O tetradentate Schiff bases capable of coordinating many metal ions. The geometry and the stereogenic group inserted in the diamine backbone or aryl aldehyde backbone have been utilized in the past to efficiently transmit chiral information in a variety of different reactions. In this review we will summarize the important and recent achievements obtained in stereocontrolled reactions in which Al(salen) metal complexes are employed. Several other reviews devoted to the general applications and synthesis of chromium and other metal salens have already been published.

Metal–organic frameworks (MOFs), as a new class of porous solid materials, have emerged and their study has established itself very quickly into a productive research field. This short review recaps the recent advancement of chiral MOFs. Here, we present simple, well-ordered instances to classify the mode of synthesis of chiral MOFs, and later demonstrate the potential applications of chiral MOFs in heterogeneous asymmetric catalysis and enantioselective separation. The asymmetric catalysis sections are subdivided based on the types of reactions that have been successfully carried out recently by chiral MOFs. In the part on enantioselective separation, we present the potentiality of chiral MOFs as a stationary phase for high-performance liquid chromatography (HPLC) and high-resolution gas chromatography (GC) by considering fruitful examples from current research work. We anticipate that this review will provide interest to researchers to design new homochiral MOFs with even greater complexity and effort to execute their potential functions in several fields, such as asymmetric catalysis, enantiomer separation, and chiral recognition.

In this study, we implemented the P,olefin-type chiral ligand (a R )-(−)- 6 , which contains a cyclohexyl group and a cinnamoyl group on the nitrogen atom, in the Pd-catalyzed asymmetric allylic amination of allylic esters with isatin derivatives 11 as nucleophiles. The reaction proceeds efficiently, yielding the products ( S )- 13 with good-to-high enantioselectivity. A scale-up reaction was also successfully conducted at a 1 mmol scale. Additionally, when malononitrile was added to the resulting product ( S )- 13a in the presence of FeCl 3 as the catalyst, the corresponding malononitrile derivative ( S )- 16 was obtained without any loss in optical purity.

The design and optimization of chiral ligands and catalysts are fundamental to advancing asymmetric catalysis, a critical area in organic chemistry with wide-ranging impacts across scientific disciplines. Traditional experimental approaches, while essential, are often hindered by their slow pace and complexity. Recent advancements have demonstrated that computational methods, particularly machine learning, offer transformative potential by significantly accelerating these processes through enhanced prediction and modeling capabilities. However, limitations such as data scarcity and model inaccuracies continue to challenge their broader application. To address these issues, we present the Chiral Ligand and Catalyst Database (CLC-DB), the first open-source, comprehensive database specifically designed for chiral ligands and catalysts. CLC-DB contains 1,861 molecules spanning 32 distinctive chiral ligand and catalyst categories, with each entry annotated with 34 types of curated information, validated by chemical experts and linked to authoritative chemical databases. The database features a user-friendly interface that supports efficient single and batch searches, as well as an integrated, high-performance online molecular clustering tool to facilitate computational analyses. CLC-DB is freely accessible at https://compbio.sjtu.edu.cn/services/clc-db , where all data are available for download. Scientific Contribution This work introduces CLC-DB, an innovative open-source database dedicated to chiral ligands and catalysts, encompassing 1,861 molecules across 32 distinct types and offering 34 types of annotated data per molecule. This resource significantly enhances data accessibility and quality for asymmetric catalysis. With its integrated molecular clustering tools and user-friendly platform, CLC-DB serves as a valuable resource for advancing the design and optimization of novel chiral ligands and catalysts.

Ionic liquids have been utilized in numerous significant applications within the field of chemistry, particularly in organic chemistry, due to their unique physical and chemical properties. In the realm of asymmetric transition-metal-catalyzed transformations, chiral ionic-liquid-supported ligands and their corresponding transition-metal complexes have facilitated these processes in unconventional solvents, especially ionic liquids and water. These innovative reaction systems enable the recycling of transition-metal catalysts while producing optically active organic molecules with comparable or even higher levels of chemo-, regio-, and stereoselectivity compared to their parent catalysts. In this short review, we aim to provide an overview of the structures of chiral ionic-liquid-supported ligands and the synthetic pathways for these ligands and catalysts. Various synthetic methodologies are demonstrated based on the conceptual frameworks of diverse chiral ionic-liquid-supported ligands. We systematically present the structures and comprehensive synthetic pathways of the chiral ionic-liquid-supported ligands and the typical corresponding transition-metal complexes that have been readily applied to asymmetric processes, categorized by their parent ligand framework. Notably, the crucial experimental procedures are delineated in exhaustive detail, with the objective of enhancing comprehension of the pivotal aspects involved in constructing chiral ionic-liquid-tagged ligands and compounds for both scholars and readers. Considering the current limitations of such ligands and catalysts, we conclude with remarks on several potential research directions for future breakthroughs in the synthesis and application of these intriguing ligands.