Multi-site programmable functionalization of alkenes via controllable alkene isomerization

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Chemistry

Background:

• Selective functionalization of hydrocarbon chains is crucial in synthetic chemistry.
• Existing methods for C=C double bonds and C(sp3)-H bonds offer limited site diversity.
• Remote functionalization via alkene isomerization and oxidative functionalization presents opportunities but faces site limitations.

Purpose of the Study:

• To develop a new method for multi-site programmable functionalization of terminal olefins.
• To achieve site-selective functionalization of both C=C double bonds and multiple C(sp3)-H bonds.
• To expand the scope of functionalized sites beyond terminal and specific internal positions.

Main Methods:

• A palladium-catalyzed aerobic oxidative method was employed.
• The strategy controlled the reaction sequence between alkene isomerization and oxidative functionalization.
• Terminal olefins were subjected to multi-site functionalization.

Main Results:

• Achieved programmable 1-acetoxylation (anti-Markovnikov), 2-acetoxylation, 1,2-diacetoxylation, and 1,2,3-triacetoxylation.
• Demonstrated controllable remote alkenylation.
• Successfully converted terminal olefins into unsaturated alcohols, polyalcohols, monosaccharides, and C-glycosides.

Conclusions:

• The developed method offers a versatile platform for complex molecule synthesis from simple olefins.
• This approach significantly enhances site diversity in hydrocarbon functionalization.
• The method provides efficient access to valuable chemical building blocks, including carbohydrates.