Synthesis of the EF-ring segment of ciguatoxin CTX1B based on novel regioselective reduction of unsaturated cyanohydrins and ring-closing olefin metathesis

A unified strategy for the synthesis of highly oxygenated diaryl ethers featured in ellagitannins

“…4) by considering the ketal and adjacent alkene as an allyl ether. This allyl ether could form its Pd-p-allyl complex and be reduced selectively [47][48][49] . Thus, Figure 5 | Syntheses of the valoneoyl (a) and tergalloyl (b) groups.…”

Transition metals in organic synthesis: Highlights for the year 2005

“…A palladium-catalyzed reductive ring-opening of an alkynyloxirane was used in a synthesis of the EF-ring segment of ciguatoxin CTX1B [599].…”

Reactivity versus Stability of Oxiranes under Palladium‐Catalyzed Reductive Conditions

“…[131] The hydrogenolysis of the epoxide can be followed by the over-reduction of the C=C bond yielding the saturated alcohol and/or its migration leading to the ketone [Equation (62)]. [132] Through the various 4,5-epoxy-2-alkenoates reduced by Shimizu, Tsuji, and coworkers, [130,[133][134][135][136] the influence of the experimental conditions on the selectivity was particularly studied by using (E)-ethyl trans-4,5-epoxy-4-methyl-5-phenyl-2-pentenoate as the substrate. [130] The catalyst induces the formation of cationic η 3 -allylpalladium complex 14A, which leads to various compounds (Scheme 15) with a selectivity depending on the nature of the ligand, Pd/L ratio (Table 11), and solvent.…”

“…Influence of the nature of hydride species on the reduction of (E)-2,3-epoxy-1-(4-methoxybenzyloxy)-4-pentene. [132] epoxide shown in Scheme 17 as a model compound. [132] As illustrated in Equation (62), the Tsuji/Shimizu procedure afforded a mixture of the saturated alcohol and the ketone.…”

“…[132] epoxide shown in Scheme 17 as a model compound. [132] As illustrated in Equation (62), the Tsuji/Shimizu procedure afforded a mixture of the saturated alcohol and the ketone. The method of Guibé led to a mixture of the homoallylic and allylic alcohols.…”