Synthesis of Seven-Membered Nitriles by Formal Anionic Divinylcyclopropane Rearrangement

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Divinylcyclopropane rearrangement is a key reaction in organic synthesis.
• Developing efficient methods for synthesizing complex cyclic compounds is crucial.

Purpose of the Study:

• To develop a novel synthetic route for 3-cyanocyclohepta-1,4-diene derivatives.
• To explore the application of divinylcyclopropane rearrangement under mild conditions.

Main Methods:

• Intramolecular alkylation of a diene with a nitrile moiety to prepare the substrate.
• Base-promoted divinylcyclopropane rearrangement under mild conditions.

Main Results:

• Successfully synthesized 3-cyanocyclohepta-1,4-diene derivatives.
• Demonstrated that heating alone was insufficient, but base treatment facilitated the rearrangement.
• Applied the developed method to the total synthesis of nardoguaianone J.

Conclusions:

• A new, mild, base-promoted method for divinylcyclopropane rearrangement was established.
• This method provides access to valuable 3-cyanocyclohepta-1,4-diene scaffolds.
• The synthetic strategy is effective for complex natural product synthesis.