The preparation, structure, and chemistry of hypervalent iodine compounds are reviewed with emphasis on their synthetic application. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. These compounds are widely used in organic synthesis as selective oxidants and environmentally friendly reagents. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, C–C bond-forming reactions, and transition metal-catalyzed reactions are summarized and discussed. Recent discovery of hypervalent catalytic systems and recyclable reagents, and the development of new enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important achievement in the field of hypervalent iodine chemistry. One of the goals of this Review is to attract the attention of the scientific community as to the benefits of...

Advances in Synthetic Applications of Hypervalent Iodine Compounds

10. Patented Literature 2616 10.1. Esterification 2616 10.2. Ether Formation 2619 10.2.1. Etherification without Cyclization 2619 10.2.2. Etherification with Cyclization 2624 10.3. N-Alkylation 2625 10.4. Other Reactions 2627 11. Summary and Outlook 2628 12. Note Added in Proof 2628 13. Abbreviations Used in This Review 2629 14. Acknowledgments 2629 15. Supporting Information Available 2630 16. References 2630

Mitsunobu and Related Reactions: Advances and Applications

Research and industrial interest in radical C–H activation/radical cross-coupling chemistry has continuously grown over the past few decades. These reactions offer fascinating and unconventional approaches toward connecting molecular fragments with high atom- and step-economy that are often complementary to traditional methods. Success in this area of research was made possible through the development of photocatalysis and first-row transition metal catalysis along with the use of peroxides as radical initiators. This Review provides a brief and concise overview of the current status and latest methodologies using radicals or radical cations as key intermediates produced via radical C–H activation. This Review includes radical addition, radical cascade cyclization, radical/radical cross-coupling, coupling of radicals with M–R groups, and coupling of radical cations with nucleophiles (Nu).

Recent Advances in Radical C-H Activation/Radical Cross-Coupling.

Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes.

Nucleophilic phosphine catalysis has proven to be a powerful tool in organic synthesis, which can provide easy access to cyclic, bicyclic or polycyclic carbocycles and heterocycles. Owing to their comparatively strong and readily tunable nucleophilicity, phosphines can be easily tailored to efficient annulation reactions with good control over reaction selectivity. This has resulted in a tremendous increase in their scope and in a concomitant number of reports where phosphine-triggered annulation reactions occur. This tutorial review summarizes the recent achievements in this area.

Phosphine-triggered synthesis of functionalized cyclic compounds

Photoredox-Catalyzed Redox-Neutral Minisci C−H Formylation of N-Heteroarenes

Self-induced stereoselective in situ trifluoromethylation: preparation of spiro[indoline-3,3'-quinoline] via palladium-catalyzed cascade reaction.

Natural tetramic acid derivatives have attracted a great deal of interest of chemists because of their structural features and the broad range of biological activities. This paper focuses on five naturally occurring tetramic acid derivatives reported to have phytotoxicity and discusses their common structural characteristics.

The phytotoxicity of natural tetramic acid derivatives

Photoredox relay-catalyzed gem-difluoroallylation of alkyl iodides.

Background Lycoris aurea (L' Herit.) Herb (Amaryllidaceae) is a native pesticide in China. The ethanolic extract of Lycoris aureate bulbs, the total alkaloids of L. aurea bulbs and the main alkaloids of L. aurea bulbs were systematically investigated as part of a novel project to study their antiviral, fungicidal (phytopathogenic) and insecticidal activities. We also prepared 18 lycorine derivatives and evaluated their bioactivities. Results Lycorine had excellent larvicidal activity against Plutella xylostella (LC50 = 10.6 mg L-1 ) and was also effective during a field trial. It also showed good inhibitory activity against tobacco mosaic virus (TMV) and good fungicidal activity against Phytophthora capsici (EC50 = 7.76 mg L-1 ). Compounds 13 and 15 exhibited good anti-TMV activity, excellent fungicidal activity against Rhizoctonia cerealis (EC50 = 6.78 mg L-1 ) and excellent larvicidal activity against Culex pipiens pallens (LC50 at 0.1-0.25 mg L-1 ). Conclusion Lycorine was identified as the main active component of L. aurea bulbs and showed potential for field application against P. xylostella. The activities of compounds 13 and 15 make them excellent candidates for new lead compounds in novel pesticide research. This study provides the basis for developing these alkaloids into potential agrochemicals. © 2018 Society of Chemical Industry.

Yuxiu Liu

Papers

Photoredox-Catalyzed Redox-Neutral Minisci C−H Formylation of N-Heteroarenes

Self-induced stereoselective in situ trifluoromethylation: preparation of spiro[indoline-3,3'-quinoline] via palladium-catalyzed cascade reaction.

The phytotoxicity of natural tetramic acid derivatives

Photoredox relay-catalyzed gem-difluoroallylation of alkyl iodides.

Leveraging botanical resources for crop protection: the isolation, bioactivity and structure-activity relationships of lycoris alkaloids.