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
Piperidine alkaloids continue to challenge the synthetic community by featuring densely functionalized scaffolds that often require careful chemical orchestration. Streptazone A and abikoviromycin are small and highly functionalized piperidine alkaloids, both accommodating Michael acceptors and a labile epoxide. These moieties are loaded into a [4.3.0] bicyclic core also present in other structurally related natural products, including the well-known piperidine alkaloid streptazolin. Here, we cover ring-closing strategies employed in earlier streptazolin syntheses; provide a concise overview of structures, biological properties, and biosyntheses of selected [4.3.0] piperidine alkaloids; and, finally, provide complete coverage of our recent asymmetric syntheses of streptazone A and abikoviromycin.1 Introduction2 Streptazolin Syntheses3 Epo-[4.3.0] Piperidine Alkaloids3.1 Streptazones3.2 Abikoviromycin3.3 Strepchazolin A and B3.4 Hatomamicin3.5 Kobutimycin A and B3.6 Camporidines A and B3.7 Epostatin3.8 N-Hydroxydihydroabikoviromycin3.9 Dihydroabikoviromycin3.10 Biosynthesis of Streptazone E and Camporidines4 Syntheses of the Streptazones and Abikoviromycin4.1 Retrosynthesis4.2 Results and Discussion5 Conclusion
Piperidine alkaloids continue to challenge the synthetic community by featuring densely functionalized scaffolds that often require careful chemical orchestration. Streptazone A and abikoviromycin are small and highly functionalized piperidine alkaloids, both accommodating Michael acceptors and a labile epoxide. These moieties are loaded into a [4.3.0] bicyclic core also present in other structurally related natural products, including the well-known piperidine alkaloid streptazolin. Here, we cover ring-closing strategies employed in earlier streptazolin syntheses; provide a concise overview of structures, biological properties, and biosyntheses of selected [4.3.0] piperidine alkaloids; and, finally, provide complete coverage of our recent asymmetric syntheses of streptazone A and abikoviromycin.1 Introduction2 Streptazolin Syntheses3 Epo-[4.3.0] Piperidine Alkaloids3.1 Streptazones3.2 Abikoviromycin3.3 Strepchazolin A and B3.4 Hatomamicin3.5 Kobutimycin A and B3.6 Camporidines A and B3.7 Epostatin3.8 N-Hydroxydihydroabikoviromycin3.9 Dihydroabikoviromycin3.10 Biosynthesis of Streptazone E and Camporidines4 Syntheses of the Streptazones and Abikoviromycin4.1 Retrosynthesis4.2 Results and Discussion5 Conclusion
A resorcinarene is a synthetic macrocycle consisting of four resorcinol molecules covalently linked by methylene bridges. The interannular bridges produce a cavitand that has a bowl-shaped structure. We have developed supramolecular capsules through Ag(I) or Cu(I) coordination-driven self-assembly of cavitands possessing 2,2′-bipyridyl arms in their upper rims. The self-assembled capsules accommodate various molecular guests and supramolecular assemblies possessing acetoxy groups. The host–guest chemistry of the molecular capsules has been applied in the fabrication of supramolecular polymers. This account describes recent developments in the supramolecular chemistry of resorcinarene-based coordination capsules and provides a brief history of resorcinarene-based capsules and related capsules.
A resorcinarene is a synthetic macrocycle consisting of four resorcinol molecules covalently linked by methylene bridges. The interannular bridges produce a cavitand that has a bowl-shaped structure. We have developed supramolecular capsules through Ag(I) or Cu(I) coordination-driven self-assembly of cavitands possessing 2,2′-bipyridyl arms in their upper rims. The self-assembled capsules accommodate various molecular guests and supramolecular assemblies possessing acetoxy groups. The host–guest chemistry of the molecular capsules has been applied in the fabrication of supramolecular polymers. This account describes recent developments in the supramolecular chemistry of resorcinarene-based coordination capsules and provides a brief history of resorcinarene-based capsules and related capsules.
A novel class of chiral multidentate ligands has been designed and synthesized from the important classic ligand 1,10-phenanthroline and amino acids. The ligands were proven to be able to coordinate with copper(2+) ion by the formation of a novel chiral copper complex, the structure of which was determined by single-crystal X-ray diffraction.
A novel class of chiral multidentate ligands has been designed and synthesized from the important classic ligand 1,10-phenanthroline and amino acids. The ligands were proven to be able to coordinate with copper(2+) ion by the formation of a novel chiral copper complex, the structure of which was determined by single-crystal X-ray diffraction.
Optical force probes (OFPs) are force-responsive molecules that report on mechanically induced transformations by the alteration of their optical properties. Yet, their modular design and incorporation into polymer architectures at desired positions is challenging. Here we report triazole-extended anthracene OFPs that combine two modular ‘click’ reactions in their synthesis potentially allowing their incorporation at desirable positions in complex polymer materials. Importantly, these retain the excellent optical properties of their parent 9-π-extended anthracene OFP counterparts.
Optical force probes (OFPs) are force-responsive molecules that report on mechanically induced transformations by the alteration of their optical properties. Yet, their modular design and incorporation into polymer architectures at desired positions is challenging. Here we report triazole-extended anthracene OFPs that combine two modular ‘click’ reactions in their synthesis potentially allowing their incorporation at desirable positions in complex polymer materials. Importantly, these retain the excellent optical properties of their parent 9-π-extended anthracene OFP counterparts.
A red-light-mediated [3+2] annulation of cyclopropylamines with akenes or alkynes in the presence of N,N′-dipropyl-1,13-dimethoxyquinacridinium is reported. An array of cyclopentane or cyclopentene derivatives with diverse functional groups have been obtained in moderate to excellent yields under mild conditions.