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

Phosphorous Acid–Assisted Electrochemical α-Tetrahydrofuranylation of Sulfonamides and Amides

A copper-catalyzed cascade reaction involving trifluoromethylation of acrylamides coupled with ring closure and indole dearomatization is reported. This facile transformation was highly regioselective and proceeded under mild conditions, allowing efficient access to trifluoromethyl-substituted spiro[indole-3,3′-pyrrolidine] derivatives, which are of increasing interest to the pharmaceutical industry.

Copper-Catalyzed Trifluoromethylation of Acrylamides Coupled with Indole Dearomatization: Access to Trifluoromethyl-Substituted Spiro[indole-3,3′-pyrrolidine] Derivatives.

A stereoselective synthesis of (+)-antofine (I) and (+)-14-hydroxyantofine (II) is presented.

Total Synthesis of Phenanthroindolizidine Alkaloids via Asymmetric Deprotonation of N‐Boc‐pyrrolidine.

A highly efficient metal-free oxidative α-cyanation reaction of N-acyl/sulfonyl tetrahydroisoquinolines under mild conditions was developed. The reaction uses 2,2,6,6-tetramethylpiperidine N-oxide fluoroborate salt (T+BF4−) as the oxidant and trimethylsilyl cyanide as the source of the cyano group.

Mild and Highly Efficient Metal‐Free Oxidative α‐Cyanation of N‐Acyl/Sulfonyl Tetrahydroisoquinolines.

The products are obtained with excellent regio- and diastereoselectivity in case of substrates bearing a symmetrically substituted phenol group, or as a mixture of two diastereomers for substrates with an nonsymmetrically substituted phenol group.

Yuxiu Liu

Papers

Phosphorous Acid–Assisted Electrochemical α-Tetrahydrofuranylation of Sulfonamides and Amides

Copper-Catalyzed Trifluoromethylation of Acrylamides Coupled with Indole Dearomatization: Access to Trifluoromethyl-Substituted Spiro[indole-3,3′-pyrrolidine] Derivatives.

Total Synthesis of Phenanthroindolizidine Alkaloids via Asymmetric Deprotonation of N‐Boc‐pyrrolidine.

Mild and Highly Efficient Metal‐Free Oxidative α‐Cyanation of N‐Acyl/Sulfonyl Tetrahydroisoquinolines.

Copper-Mediated α-Trifluoromethylation of N-Phenylcinnamamides Coupled with Dearomatization: Access to Trifluoromethylated 1-Azaspiro[4.5]decanes.