Total Synthesis of Bryostatin 8 Using an Organosilane‐Based Strategy

Abstract

Convergent total synthesis of bryostatin 8h as been accomplished by an organosilane-based strategy.The Cring is constructed stereoselectively through ag eminal bis(silane)based [1,5]-Brook rearrangement, and the Bring through geminal bis(silane)-based Prins cyclization, thus efficiently joining the northern and southern parts of the molecule. Scheme 1. Structure of bryostatins 1-21.

Silylarene Hydrogenation: A Strategic Approach that Enables Direct Access to Versatile Silylated Saturated Carbo‐ and Heterocycles

“…[3] Furthermore,a lkoxy-and halosilyl groups are prone to nucleophilic cleavage of the SiÀXb ond and the large steric demand of silicon substituents can hinder productive coordination of the arene to the catalyst. [4] A general method that overcomes those challenges would be of interest because (alkyl)silyl groups are widely employed in organic synthesis [5] as reagents [6] or for structure elaboration by am yriad of transformations such as Hiyama couplings, Fleming-Tamao oxidations,o rB rook rearrangements. [7] Alkoxy-and halosilyl groups are used in materials science, for example,f or the preparation of polymers and inorganicorganic hybrid materials.…”

Synthesis of Heterocyclic Scaffolds via Prins, Oxonium-Ene and Related Cyclization Reactions

“…Meanwhile, Rychnovsky and Bahnck synthesized the macrolide (–)-kendomycin 13 by using a Prins cyclization reaction. Bryostatins 1 and 8, which are naturally occurring complex molecular structures, were synthesized by the Keck 14 and Zhang 15 groups. Zhang’s group have described a vinylogous Mannich and an intramolecular Heathcock/aza-Prins cyclization strategy for the total synthesis of the structurally complex alkaloid (–)-vindoroisine.…”