Studies on the synthesis of pectenotoxin II: synthesis of a C(11)-C(26) fragment precursor via [3 + 2]-annulation reactions of chiral allylsilanes.

[see reaction]. A synthesis of tetracycle 2 corresponding to the C(11)-C(26) fragment of pectenotoxin II is described. The synthesis features two highly stereoselective [3 + 2]-annulation reactions of chiral allylsilanes, generated via allylboration of aldehydes with the chiral gamma-silylallylborane 4 or the gamma-silylallylboronate 19, for construction of the highly substituted C and E rings.

Synthesis of the C(29)-C(45) bis-pyran subunit (E-F) of spongistatin 1 (Altohyrtin A).

A synthesis of the C(29)-C(45) bis-pyran subunit 2 of spongistatin 1 (1a) is described. The synthesis proceeds in 19 steps from the chiral aldehyde ent-7, and features highly diastereoselective alpha-alkoxyallylation reactions using the gamma-alkoxy substituted allylstannanes 17 and 19, as well as a thermodynamically controlled intramolecular Michael addition to close the F-ring pyran. The E ring was assembled via the Mukaiyama aldol reaction of F-ring methyl ketone 3 and the 2,3-syn aldehyde 4.

A three-component coupling strategy for tetrahydrofuran synthesis: application of the diisopropyl tartrate modified (E)-gamma-(dimethylphenylsilyl)allylboronate as an alpha,gamma-allyl dianion equivalent.

[reaction: see text] A highly convergent three-component coupling strategy for the stereocontrolled synthesis of 2,3,5-trisubstituted tetrahydrofurans is described. After allylboration of the first aldehyde with 1, the chiral, nonracemic allylsilanes 2 are coupled with a second aldehyde or ketone with Lewis acid catalysis to give tetrahydrofurans 3 or 4 with excellent selectivity. The 2,5-stereochemistry is controlled by operating under nonchelate (e.g., 3) or chelate (e.g., 4) conditions.