1379679-84-1Relevant academic research and scientific papers
Concise synthesis of norrisolide
Granger, Krista,Snapper, Marc L.
, p. 2308 - 2311 (2012)
The marine natural product norrisolide has been synthesized in a convergent manner with a longest linear sequence of 14 steps. The hydrindane portion of the molecules is prepared through conjugate addition of a functionalized allyl group into cyclopentenone, followed by stereoselective trapping of the enolate generated from the resulting enol silyl ether with an allyl electrophile. Ring-closing metathesis then establishes the 6-5 ring system. Likewise, selective preparation of the side chain features an enantioselective cyclopropanation of furan-2-one, followed by rearrangement and hydrogenation. Coupling of the two major fragments through a Shapiro reaction, followed by reduction and olefination then completes the carbon framework of the natural product. The final steps of the synthesis involve adjustments to the oxidation state of the side chain. New strategies to generate both the hydrindane core and the oxidized side chain has allowed for the more concise and efficient preparation of the natural product. A new strategy to prepare Norrisolide's hydrindane core, as well as the oxidized side chain, has allowed for a more concise and efficient preparation of the natural product. The significantly abbreviated synthetic sequences to these fragments will allow for more facile preparations of related natural product targets.
Total Synthesis of (-)-Chromodorolide B by a Computationally-Guided Radical Addition/Cyclization/Fragmentation Cascade
Tao, Daniel J.,Slutskyy, Yuriy,Muuronen, Mikko,Le, Alexander,Kohler, Philipp,Overman, Larry E.
, p. 3091 - 3102 (2018/03/08)
The first total synthesis of a chromodorolide marine diterpenoid is described. The core of the diterpenoid is constructed by a bimolecular radical addition/cyclization/fragmentation cascade that unites two complex fragments and forms two C-C bonds and four contiguous stereogenic centers of (-)-chromodorolide B in a single step. This coupling step is initiated by visible-light photocatalytic fragmentation of a redox-active ester, which can be accomplished in the presence of an iridium or a less-precious electron-rich dicyanobenzene photocatalyst, and employs equimolar amounts of the two addends. Computational studies guided the development of this central step of the synthesis and provide insight into the origin of the observed stereoselectivity.
