DualPhos: a versatile, chemoselective reagent for two-carbon aldehyde to latent ( E )-alkenal homologation and application in the total synthesis of phomolide G

Abstract

Advances on the use of the 2-pinacolacetal-tripropylphosphonium salt DualPhos as a general reagent for the two-carbon aldehyde to alkenal homologation and a chemoselective iron (III) chloride mediated deprotection are described. The strategy allows isolation of the latent alkenal intermediates or direct hydrolysis to (E)-alkenals. The robust chemical stability of the latent alkenals is demonstrated in a total synthesis of the macrolactone phomolide G.

Natural ten-membered lactones: sources, structural diversity, biological activity, and intriguing future

“…In the case when the potent compound is unavailable as a natural product, it is rational to develop a scheme for its chemical synthesis. Some TMLs can be obtained by total synthesis, 77,[128][129][130] but the synthetic studies usually do not consider the biological activity of the products and do not enrich the data about its biological activity. The main synthetic approaches used to construct different TMLs were described in the previous reviews by Dräger et al (1996) 1 and Sun et al Natural Product Reports Review (2012).…”

Highly Selective Rhodium Catalyzed 1,4‐Hydrogenation of Conjugated Dienals

“…Herein, we would like to report the development of a rhodium catalyzed unprecedented regio‐ and chemoselective directing group free hydrogenation of conjugated dienals into the corresponding γ,δ‐unsaturated aldehydes [25] . The conjugated dienals can be conveniently obtained by several known synthetic methods such as the Wittig‐Horner‐Emmons reactions ( A – B ), [26a–c] the addition of ethoxy‐vinyl zinc reagents ( C ) [26d] and the Müller‐Cunradi‐Pieroh reaction ( D ), [26e–g] as shown in Scheme 3.…”