posted on 2021-02-03, 15:06authored byStephan N. Hess, Xiaobin Mo, Conny Wirtz, Alois Fürstner
A nonthermodynamic array of four skipped methylene substituents
on the hydrophobic tail renders limaol, a C40-polyketide of marine
origin, unique in structural terms. This conspicuous segment was assembled
by a two-directional approach and finally coupled to the polyether
domain by an allyl/alkenyl Stille reaction under neutral conditions.
The core region itself was prepared via a 3,3′-dibromo-BINOL-catalyzed
asymmetric propargylation, a gold-catalyzed spirocyclization, and
introduction of the southern sector via substrate-controlled allylation
as the key steps.