Total Synthesis of (−)-Mandelalide A Exploiting Anion Relay Chemistry (ARC): Identification of a Type II ARC/CuCN Cross-Coupling Protocol
نویسندگان
چکیده
Anion relay chemistry (ARC), an effective, multicomponent union tactic, was successfully employed for the total synthesis of the highly cytotoxic marine macrolide (-)-mandelalide A (1). The northern hemisphere was constructed via a new type II ARC/CuCN cross-coupling tactic, while the southern hemisphere was secured via a highly efficient four-component type I ARC union. Importantly, the synthesis of 1 showcases ARC as a rapid, scalable coupling strategy for the union of simple readily available building blocks to access diverse complex molecular fragments with excellent stereochemical control.
منابع مشابه
Total Synthesis of (−)-Secu’amamine A Exploiting Type II Anion Relay Chemistry
A total synthesis of (-)-secu'amamine A has been achieved exploiting Type II Anion Relay Chemistry (ARC) to provide the full linear carbon and nitrogen skeleton in a single flask with the requisite stereochemistry and functionality. A mechanistic rationale is also proposed to account for the stereochemical outcome of the key aldol reaction leading to the advanced aza tricyclic core.
متن کاملDiversity-oriented synthesis leads to an effective class of bifunctional linchpins uniting anion relay chemistry (ARC) with benzyne reactivity.
In conjunction with the construction of a diversity-oriented synthesis library of 10-membered ring "natural product-like" macrolides, the design, synthesis, and validation of a unique class of bifunctional linchpins, uniting benzyne reactivity initiated by type II anion relay chemistry (ARC) has been achieved, permitting access to diverse [2+2], [3+2], and [4+2] cycloadducts.
متن کاملTotal Synthesis of (−)-Enigmazole A
A highly convergent, stereocontrolled total synthesis of the architecturally complex marine sponge metabolite (-)-enigmazole A has been achieved. Highlights include an unprecedented late-stage large-fragment Petasis-Ferrier union/rearrangement, a multicomponent Type I Anion Relay Chemistry (ARC) tactic, and a dithiane-epoxide union in conjunction with an oxazole-directed stereoselective reduction.
متن کاملThe [1,5]-Brook rearrangement: an initial application in anion relay chemistry.
The [1,5]-Brook rearrangement proceeds efficiently in a series of hydroxyl dithiane substrates with sodium and potassium bases; less effective are lithium bases. That the mode of silyl migration is intramolecular was demonstrated by a crossover experiment. Finally, the tricomponent anion relay chemistry (ARC) coupling tactic was demonstrated employing the [1,5]-Brook rearrangement.
متن کاملSynthesis and characterization of MCM-41@L-arginine@Pd(0) and its excellent catalytic activity as recyclable heterogeneous catalyst for Suzuki-Miyaura cross-coupling reaction
MCM-41@L-Arg@Pd(0) has been prepared by some consequence reactions. This nano structural material has been characterized via different technique including: XRD, TGA, BET, EDS, X-Ray maps, SEM, ICP-OES and FT-IR analysis. The synthesis of a variety of biphenyl compounds has been achieved successfully via a reaction of aryl halides with arylboronic acids in the presence of this nanostructure (MCM...
متن کامل