Aerial dioxygen activation vs. thiol-ene click reaction within a system

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Carbon-sulfur (C-S) bond formation is crucial in organic synthesis.
• Styrenes and thiophenols are common building blocks for C-S bond formation.
• Existing methods include Markovnikov and anti-Markovnikov selective thiol-ene click (TEC) reactions and synthesis of β-hydroxysulfides via aerial dioxygen activation.

Purpose of the Study:

• To develop a versatile method for selective C-S bond formation.
• To control the outcome of reactions between styrenes and thiophenols.
• To achieve exclusive synthesis of target products in high yields.

Main Methods:

• Optimization of reaction conditions, including solvent choice and additives.
• Exploration of neat reaction conditions.
• Utilizing aerial dioxygen activation for specific transformations.

Main Results:

• Exclusive achievement of Markovnikov selective thiol-ene click (TEC) reaction.
• Exclusive achievement of anti-Markovnikov selective thiol-ene click (TEC) reaction.
• Exclusive synthesis of β-hydroxysulfides via aerial dioxygen activation.
• All reactions proceeded in excellent yields.

Conclusions:

• The developed methodology allows for precise control over C-S bond formation pathways.
• Reaction environment is key to selectively directing the outcome between TEC and β-hydroxysulfide synthesis.
• This work provides a powerful and flexible approach to synthesizing valuable sulfur-containing organic compounds.