Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Green Chemistry

Background:

• Hypervalent iodine(III) compounds are recognized for their utility as environmentally benign reagents and catalysts in modern organic chemistry.
• These reagents are pivotal in synthetically crucial reactions including halogenations, oxidations, aminations, heterocyclizations, and oxidative functionalizations.

Purpose of the Study:

• To review recent advancements in hypervalent iodine chemistry, focusing on developments from 2016 to 2024.
• To highlight the unique chemical transformations enabled by hypervalent iodine reagents that are often unachievable with other reagents.

Main Methods:

• Review of literature published between 2016 and 2024.
• Analysis of applications of various hypervalent iodine derivatives, including benziodoxoles, in group transfer reactions.
• Examination of catalytic systems, including transition metal catalysis, metal-free conditions, and photocatalysis.

Main Results:

• Iodonium salts serve as key arylating agents, while iodonium ylides and imides are effective carbene and nitrene precursors.
• Benziodoxole derivatives (e.g., azido-, trifluoromethyl-, alkynyl-, alkenyl-) are widely used as group transfer reagents.
• Significant progress has been made in developing hypervalent iodine catalytic systems and highly enantioselective reactions using chiral hypervalent iodine compounds.

Conclusions:

• Hypervalent iodine chemistry continues to evolve, offering unique and sustainable synthetic methodologies.
• The development of catalytic and enantioselective hypervalent iodine reactions represents a major achievement, expanding the synthetic chemist's toolkit.