ja510768c_si_001.pdf (7.86 MB)
Preparation of Macrocyclic Z‑Enoates and (E,Z)- or (Z,E)‑Dienoates through Catalytic Stereoselective Ring-Closing Metathesis
journal contribution
posted on 2015-12-17, 06:04 authored by Hanmo Zhang, Elsie
C. Yu, Sebastian Torker, Richard R. Schrock, Amir H. HoveydaThe
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.