Through-bond/through-space anion relay chemistry exploiting vinylepoxides as bifunctional linchpins

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Anion relay chemistry (ARC) is a powerful synthetic tool.
• Developing versatile bifunctional linchpins is crucial for expanding ARC's utility.
• Existing linchpins may have limitations in uniting diverse building blocks.

Purpose of the Study:

• To design, synthesize, and validate novel vinylepoxide linchpins for ARC.
• To explore the application of these linchpins in both through-bond and through-space ARC.
• To investigate the stereochemical outcomes of reactions utilizing these linchpins.

Main Methods:

• Synthesis of three distinct vinylepoxide linchpins: trans-disubstituted, cis-disubstituted, and trans-trisubstituted.
• Application of these linchpins in anion relay chemistry involving SN 2' reaction and 1,4-Brook rearrangement.
• Analysis of reaction products to determine stereoselectivity (E/Z isomer ratios).

Main Results:

• Successful synthesis and validation of the three vinylepoxide linchpins.
• Demonstration of sequential through-bond (SN 2') and through-space (1,4-Brook rearrangement) ARC.
• The cis-disubstituted and trans-trisubstituted vinylepoxide linchpins yielded three-component adducts with high E-selectivity.
• The trans-disubstituted linchpin resulted in a mixture of E/Z isomers.

Conclusions:

• Vinylepoxide linchpins are effective bifunctional tools for anion relay chemistry.
• Stereochemistry of the linchpin significantly influences the selectivity of the ARC process.
• These linchpins offer a promising route for constructing complex molecular architectures with controlled stereochemistry.