Synlett

Asymmetric organocatalysis is emerging as an elegant tool for accelerating chemical reactions and creating specific types of molecules. Chiral Brønsted acid catalysis is an important area of organocatalysis. We recently described an intramolecular iminium-ion cyclization reaction of 2-alkenylbenzaldimines catalyzed by a chiral Brønsted acid (a BINOL-derived N-triflylphosphoramide) for the synthesis of chiral 1-aminoindenes and tetracyclic 1-aminoindanes in good yields and high enantioselectivities. One of the resulting 1-aminoindenes is a useful intermediate for the synthesis of (S)-rasagiline, an effective drug for the symptomatic treatment of Parkinson’s disease. Moreover, some tetracyclic 1-aminoindanes are present in the skeletons of homoisoflavanoid natural products such as brazilin.

This Account covers the recent progress made on heterocyclic mechanophores in the field of polymer mechanochemistry. In particular, the types of such mechanophores as well as the mechanisms and applications of their force-induced structural transformations are discussed and related perspectives and future challenges proposed.1 Introduction2 Types of Mechanophores3 Methods to Incorporate Heterocycle Mechanophores into Polymer Systems4 Mechanochemical Reactions of Heterocyclic Mechanophores4.1 Three-Membered-Ring Mechanophores4.2 Four-Membered-Ring Mechanophores4.3 Six-Membered-Ring Mechanophores4.4 Bicyclic Mechanophores5 Applications5.1 Cross-Linking of Polymer5.2 Degradable Polymer5.3 Mechanochromic Polymer6 Concluding Remarks and Outlook

This Account covers the recent progress made on heterocyclic mechanophores in the field of polymer mechanochemistry. In particular, the types of such mechanophores as well as the mechanisms and applications of their force-induced structural transformations are discussed and related perspectives and future challenges proposed.1 Introduction2 Types of Mechanophores3 Methods to Incorporate Heterocycle Mechanophores into Polymer Systems4 Mechanochemical Reactions of Heterocyclic Mechanophores4.1 Three-Membered-Ring Mechanophores4.2 Four-Membered-Ring Mechanophores4.3 Six-Membered-Ring Mechanophores4.4 Bicyclic Mechanophores5 Applications5.1 Cross-Linking of Polymer5.2 Degradable Polymer5.3 Mechanochromic Polymer6 Concluding Remarks and Outlook

In this paper, ynolate-initiated cycloaddition (annulation) to form a range of carbocycles and heterocycles is described. Ynolates consist of a ketene anion equivalent, which contains both nucleophilic and electrophilic moieties, and a carbodianion equivalent that achieves double addition. Hence, in addition to the usual [n+2] cycloaddition, ynolates can perform formal [n+1]-type annulations. Their high-energy performance has been demonstrated by their triple addition to arynes to generate triptycenes, in which the C–C triple bond of ynolates is cleaved. The synthetic applications of these methods, including natural products synthesis, are also described.1 Introduction2 Preparation of Ynolates2.1 Double Lithiation2.2 Flow Synthesis2.3 Double Deprotonation3 [2+2] Cycloaddition to C=O Bond3.1 To Aldehydes and Ketones3.2 Sequential Cycloaddition4 [2+2] Cycloaddition to Imino Groups

In this paper, ynolate-initiated cycloaddition (annulation) to form a range of carbocycles and heterocycles is described. Ynolates consist of a ketene anion equivalent, which contains both nucleophilic and electrophilic moieties, and a carbodianion equivalent that achieves double addition. Hence, in addition to the usual [n+2] cycloaddition, ynolates can perform formal [n+1]-type annulations. Their high-energy performance has been demonstrated by their triple addition to arynes to generate triptycenes, in which the C–C triple bond of ynolates is cleaved. The synthetic applications of these methods, including natural products synthesis, are also described.1 Introduction2 Preparation of Ynolates2.1 Double Lithiation2.2 Flow Synthesis2.3 Double Deprotonation3 [2+2] Cycloaddition to C=O Bond3.1 To Aldehydes and Ketones3.2 Sequential Cycloaddition4 [2+2] Cycloaddition to Imino Groups

The Account describes recent advances, from the authors’ laboratories, in the synthesis of diverse libraries of small-molecule building blocks employing ionic liquids (ILs). The ability of ILs to act as catalysts/promoters/solvents for electrophilic and onium ion chemistry, as well as in metal-mediated cross-coupling reactions, and the potential to sequence/hyphenate these methods, have opened up new opportunities for facile assembly of functional small molecules with increased complexity from readily available precursors. While Brønsted acidic IL/IL solvent mixtures are suitable media for carbocation and onium ion chemistry, piperidine-appended IL/IL solvent mixtures can successfully catalyze a variety of base-catalyzed reactions. Several widely practiced transformations including ‘name reactions’ were adapted and performed efficiently in ILs.1 Introduction2 Aryldiazonium Salts and Aryltriazenes as Coupling Partners in Metal-Mediated C–C Cross-Coupling Reactions in ILs3 Expanding the Scope of Metal-Mediated Cross-Coupling Reactions in ILs4 Application of ILs in Synthesis and Functionalization of Hetero­cycles5 Expanding the Scope of Amide Synthesis in ILs6 Generation and Chemistry of ‘Tamed’ Propargylic Cations in ILs7 Newer Nitration Methods for Arenes and Heteroarenes in ILs8 Halofunctionalization in ILs9 ‘Name Reactions’and Other Widely Practiced Synthetic Transformations in ILs9.1 The Biginelli Reaction9.2 Nitrile Synthesis by the Schmidt Reaction9.3 Rupe Rearrangement9.4 Synthesis of 1,3-Dioxanes via Prins Reaction in [BMIM(SO3H)][OTf]9.5 Synthesis of Cyclopropanes and Oxiranes by the Corey–Chaykovsky (CC) Reaction10 Conclusions and Closing Remarks

The Account describes recent advances, from the authors’ laboratories, in the synthesis of diverse libraries of small-molecule building blocks employing ionic liquids (ILs). The ability of ILs to act as catalysts/promoters/solvents for electrophilic and onium ion chemistry, as well as in metal-mediated cross-coupling reactions, and the potential to sequence/hyphenate these methods, have opened up new opportunities for facile assembly of functional small molecules with increased complexity from readily available precursors. While Brønsted acidic IL/IL solvent mixtures are suitable media for carbocation and onium ion chemistry, piperidine-appended IL/IL solvent mixtures can successfully catalyze a variety of base-catalyzed reactions. Several widely practiced transformations including ‘name reactions’ were adapted and performed efficiently in ILs.1 Introduction2 Aryldiazonium Salts and Aryltriazenes as Coupling Partners in Metal-Mediated C–C Cross-Coupling Reactions in ILs3 Expanding the Scope of Metal-Mediated Cross-Coupling Reactions in ILs4 Application of ILs in Synthesis and Functionalization of Hetero­cycles5 Expanding the Scope of Amide Synthesis in ILs6 Generation and Chemistry of ‘Tamed’ Propargylic Cations in ILs7 Newer Nitration Methods for Arenes and Heteroarenes in ILs8 Halofunctionalization in ILs9 ‘Name Reactions’and Other Widely Practiced Synthetic Transformations in ILs9.1 The Biginelli Reaction9.2 Nitrile Synthesis by the Schmidt Reaction9.3 Rupe Rearrangement9.4 Synthesis of 1,3-Dioxanes via Prins Reaction in [BMIM(SO3H)][OTf]9.5 Synthesis of Cyclopropanes and Oxiranes by the Corey–Chaykovsky (CC) Reaction10 Conclusions and Closing Remarks

The cyclopropanation of alkenes through the transition-metal-catalyzed decomposition of diazo compounds is a powerful and straightforward strategy to produce cyclopropanes. Nevertheless, the appeal of further application of this strategy is tempered by the potentially explosive nature of the diazo substrates. Therefore, it is highly desirable to develop sustainable and operationally safe surrogates for diazo compounds. In this Synpacts article, we discuss recent advances on the cyclopropane syntheses through the catalytic cyclopropanation of alkenes and metal carbenes generated in situ from nondiazo precursors as well as highlight our recent progress on the unprecedented molybdenum-catalyzed deoxygenative cyclopropanation reaction of 1,2-dicarbonyl or monocarbonyl compounds.

The cyclopropanation of alkenes through the transition-metal-catalyzed decomposition of diazo compounds is a powerful and straightforward strategy to produce cyclopropanes. Nevertheless, the appeal of further application of this strategy is tempered by the potentially explosive nature of the diazo substrates. Therefore, it is highly desirable to develop sustainable and operationally safe surrogates for diazo compounds. In this Synpacts article, we discuss recent advances on the cyclopropane syntheses through the catalytic cyclopropanation of alkenes and metal carbenes generated in situ from nondiazo precursors as well as highlight our recent progress on the unprecedented molybdenum-catalyzed deoxygenative cyclopropanation reaction of 1,2-dicarbonyl or monocarbonyl compounds.

Sulfoxides are important organic synthons that have been used in a variety of transformations. In this account, we focus on advances in the reaction of sulfoxides with benzynes, which can be divided into two types: benzyne ortho-difunctionalization and benzyne multifunctionalization.1 Introduction2 Benzyne ortho-Difunctionalization3 Benzyne Multifunctionalization4 Conclusion