Rearrangements Induced by Hypervalent Iodine.

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Reaction Mechanisms

Background:

• Hypervalent iodine reagents have emerged as versatile tools in organic synthesis.
• The period between 2004 and 2015 witnessed significant advancements in iodine(III)-mediated transformations.
• Understanding these rearrangements is crucial for developing new synthetic methodologies.

Purpose of the Study:

• To provide a comprehensive overview of hypervalent iodine(III)-induced rearrangements reported between 2004 and 2015.
• To highlight key reaction types, including Hofmann-type rearrangements, aryl transpositions, and phenol dearomatization-triggered processes.
• To discuss stereoselective transformations and novel tandem reactions involving hypervalent iodine.

Main Methods:

• Review of literature published between 2004 and 2015 focusing on hypervalent iodine chemistry.
• Categorization of rearrangements based on reaction type and mechanistic pathways.
• Analysis of stereochemical outcomes and synthetic applications.

Main Results:

• Detailed description of Hofmann-type rearrangements and aliphatic aryl transpositions using iodine(III) reagents.
• Exploration of Wagner-Meerwein-type rearrangements, Prins-pinacol transpositions, and tandem polycyclization-pinacol processes triggered by phenol dearomatization.
• Inclusion of other significant rearrangements like iodonio-Claisen and ipso-rearrangements, as well as iodine(V)-mediated reactions.

Conclusions:

• Hypervalent iodine(III) chemistry offers diverse and efficient routes for complex molecular transformations.
• Stereoselective control and novel cascade reactions have been achieved using these methodologies.
• The field continues to evolve, presenting opportunities for further synthetic innovation.