Preparation of macrocyclic Z-enoates and (E,Z)- or (Z,E)-dienoates through catalytic stereoselective ring-closing metathesis.
- Author(s): Zhang, Hanmo
- Yu, Elsie C
- Torker, Sebastian
- Schrock, Richard R
- Hoveyda, Amir H
- et al.
Published Web Locationhttps://doi.org/10.1021/ja510768c
The first examples of catalyst-controlled stereoselective macrocyclic ring-closing metathesis reactions that generate Z-enoates as well as (E,Z)- or (Z,E)-dienoates are disclosed. Reactions promoted by 3.0-10 mol % of a Mo-based monoaryloxide pyrrolide complex proceed to completion within 2-6 h at room temperature. The desired macrocycles are formed in 79:21 to >98:2 Z/E selectivity; stereoisomerically pure products can be obtained in 43-75% yield after chromatography. Utility is demonstrated by application to a concise formal synthesis of the natural product (+)-aspicilin.