Thiyl Radicals: Versatile Reactive Intermediates for Cyclization of Unsaturated Substrates

Area of Science:

• Organic Chemistry
• Radical Chemistry

Background:

• Sulfur-centered radicals, particularly thiyl radicals, are crucial for hydrothiolation reactions.
• Thiyl radicals offer a sustainable alternative to toxic organotin-based methods in chemical synthesis.
• Radical chain processes involving thiyl radicals are effective for creating thioether bioconjugates.

Purpose of the Study:

• To review the development of thiyl radicals as initiators for carbocyclization cascades.
• To highlight key advancements in cascade cyclization methodology using thiyl radicals.
• To discuss the applications of these methods in natural product synthesis.

Main Methods:

• Chronological review of literature from the 1970s to present.
• Focus on radical chain processes and cascade reactions.
• Analysis of thiyl radical generation and reactivity.

Main Results:

• Thiyl radicals are versatile intermediates for initiating complex molecular constructions.
• Cascade reactions involving thiyl radicals enable efficient synthesis of carbocyclic frameworks.
• Significant progress has been made in applying these methods to natural product synthesis.

Conclusions:

• Thiyl radical chemistry has evolved significantly over five decades.
• These methods provide powerful tools for constructing complex organic molecules.
• The review underscores the importance of thiyl radicals in modern synthetic chemistry.