Total Synthesis of (−)‐Basiliskamide B

Abstract

The total synthesis of the polyketide antibiotic (À)-basiliskamide B is described. The convergent asymmetric synthesis relies on the use of a diastereoselective ethyl ketone aldol reaction followed by a syn selective reduction of a b-hydroxy ketone and a Stille cross-coupling between a Z-vinylstannane and an E-vinyl iodide to establish the

Baker's Yeast Reduction of β‐Hydroxy Ketones

“…The chiral molecules that organic chemists are called on to prepare today show such stereochemical complexity that the configuration of more than one stereogenic centre often has to be controlled 6. The synthesis of configurationally defined steric sequences such as 1,3‐diols or 2‐alkyl‐1,3‐diols, for example, is a challenging task that can be achieved through highly stereoselective 1,3‐diketone or 3‐hydroxy ketone reductions 7. The concomitant formation of stereogenic centres of precise configuration in one‐pot transformations is of great advantage from a synthetic point ofview.…”

α-Silicon effect assisted Curtin–Hammett allylation using allylcopper reagents derived from 1,3-dienylsilanes

“…Pd-catalyzed Stille-coupling of vinyl iodide 12 with ( E )-vinyl stannane 13 29 gave product 14 in 81% yield, which corresponds to the C 1–9 fragment of the polyketide natural product mycinolide IV. In addition, Pd-catalyzed cross-coupling of 12 and ( Z )-vinyl stannane 15 30 delivered diene 16 in 85% yield. Sonogashira coupling of 17 with ethyl propiolate ( 18 ) furnished enyne 19 in 81% yield 31…”

Stereoselective Construction of (E,Z)‐1,3‐Dienes and Its Application in Natural Product Synthesis

“…[50] The Stille-type cross-coupling was also illustrated in the total syntheses of basiliskamides A and B by Panek and Dias. [54,55] Another strategy, proposed by Yadav, relied on a Stille-type cross-coupling reaction of a Z-vinyl iodide fragment (obtained by a Stork-Zhao olefination) and E-vinyl stannane intermediate (synthesised via hydrostannation) to obtain a diacetonide analogue of thuggacin A. [56] During the synthesis of (À )-archazolid B, Trauner combined an E,Z-vinyl stannane with a Z-vinyl iodide to install the sensitive Z,Z,E-triene unit during the endgame transformations to avoid potential (cyclo)isomerisations.…”