Ligand‐Controlled Divergent Synthesis of cis/trans ‐Trisubstituted Cycloalkenes via Pd‐Catalyzed [6+4] Cyclization
Abstract
Medium-sized cycloalkenes are pivotal motifs in natural products and bioactive molecules, yet the divergent and stereoselective synthesis of their cis- and trans-isomers remains a long-standing challenge. To address this, we present a ligand-controlled, Pd-catalyzed [6+4] dipolar cyclization between N-PMB vinyl carbamates and azadienes that enables the divergent synthesis of both cis- and trans-trisubstituted 10-membered cycloalkenes. The key to this success is the ligand-modulated stability of the cis- and trans-π-allyl-Pd dipolar intermediates, allowing for high stereoselectivity by a simple switch of the phosphine ligand. This strategy provides a versatile and efficient platform for precisely constructing challenging medium-sized cycloalkenes with controlled olefin geometry.
Fields of Study & Subjects
Catalytic C–H Functionalization Methods
Catalytic Alkyne Reactions
Cyclopropane Reaction Mechanisms
Publication details
- Journal / source
- Chemistry - An Asian Journal
- Publisher
- Wiley
- Volume
- 21
- Issue
- 10
- Pages
- e70680–e70680
- Publication date
- 1 May 2026
- Language
- EN