合成脱水岩兰草醇。
Synthesis of Anhydroryanodol.
机构信息
Department of Chemistry, Burke Laboratory, Dartmouth College, Hanover, New Hampshire 03755, United States.
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
出版信息
J Am Chem Soc. 2020 Jul 29;142(30):12937-12941. doi: 10.1021/jacs.0c05766. Epub 2020 Jul 7.
A stereoselective entry to ryanoids is described that culminates in the synthesis of anhydroryanodol and thus the formal total synthesis of ryanodol. The pathway described features an annulation reaction conceived to address the uniquely complex and highly oxygenated polycyclic skeleton common to members of this natural product class. It is demonstrated that metallacycle-mediated intramolecular coupling of an alkyne and a 1,3-diketone can proceed with a highly functionalized enyne and with outstanding levels of stereoselection. Furthermore, the first application of this technology in natural product synthesis is demonstrated here. More broadly, the advances described demonstrate the value that programs in natural product total synthesis have in advancing organic chemistry, here through the design and realization of an annulation reaction that accomplishes what previously established reactions do not.
描述了一种立体选择性进入瑞诺类化合物的方法，该方法以合成无水瑞诺醇为终点，从而完成了瑞诺醇的正式全合成。所描述的途径具有环化反应，旨在解决此类天然产物中普遍存在的独特复杂和高度氧化的多环骨架。结果表明，金属环介导的炔烃和 1,3-二酮的分子内偶联可以与高度官能化的烯炔和出色的立体选择性进行。此外，还在这里首次展示了该技术在天然产物合成中的应用。更广泛地说，所描述的进展表明天然产物全合成计划在推进有机化学方面具有重要价值，这里通过设计和实现一种环化反应来实现以前的反应无法实现的目标。
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