Divergence en Route to Nonclassical Annonaceous Acetogenins. Synthesis of Pyranicin and Pyragonicin
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 5, 1879-1891 p.Article in journal (Refereed) Published
Syntheses of the nonclassical annonaceous acetogenins, pyranicin, and pyragonicin from common late-stage intermediates are presented. The construction of key elements relies on asymmetric HWE reactions, including the desymmetrization of a meso-dialdehyde and a parallel kinetic resolution of a racemic aldehyde. A stereoconvergent Pd-catalyzed substitution serves to install the C4 stereocenter in protected form with different orthogonal protective groups. A divergent strategy to form 1.4- and 1.6-diols, employing stereoselective Zn-mediated alkynylations, is used for completion of the core structures. Notably, the stereoselective coupling reaction toward pyragonicin proceeds with highly functionalized fragments. The methodology is further expanded by a divergent synthesis of all stereoisomers of the 2,3,6-trisubstituted tetrahydropyran subunit.
Place, publisher, year, edition, pages
2006. Vol. 71, no 5, 1879-1891 p.
horner-wadsworth-emmons, molecular mechanics, tetrahydropyran ring, cytotoxic acetogenin, recent progress, complex-i, efficient, stereodivergent, aldehydes, ethers
IdentifiersURN: urn:nbn:se:kth:diva-6068DOI: 10.1021/jo05223kISI: 000235896800015ScopusID: 2-s2.0-33644652277OAI: oai:DiVA.org:kth-6068DiVA: diva2:10671
QC 201009212006-08-282006-08-282010-09-21Bibliographically approved