Dangalov Miroslav, Fernández-Figueiras Adolfo, Ravutsov Martin A, Vakarelska Ekaterina, Marinova Maya K, Candeias Nuno R, Simeonov Svilen P
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl 9, Sofia 1113, Bulgaria.
LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
ACS Catal. 2023 Jan 18;13(3):1916-1925. doi: 10.1021/acscatal.2c04867. eCollection 2023 Feb 3.
A Ru-catalyzed isomerization of Achmatowicz derivatives that opens unexplored routes to diversify the biogenic furanic platform is reported. The mechanistic insights of this formally redox-neutral intramolecular process were studied computationally and by deuterium labeling. The transformation proved to be a robust synthetic tool to achieve the synthesis of bioderived-monomers and a series of 4-keto-δ-valerolactones that further enabled the development of a flexible strategy for the synthesis of acetogenins. A concise and protective group-free asymmetric total synthesis of two natural products, namely, (,)-muricatacin and the (,)-L-factor, is also described.
报道了一种钌催化的阿赫马托维奇衍生物的异构化反应，该反应开辟了未被探索的途径，使生物源呋喃平台多样化。通过计算和氘标记研究了这个形式上氧化还原中性的分子内过程的机理。该转化被证明是一种强大的合成工具，可用于实现生物衍生单体和一系列4-酮基-δ-戊内酯的合成，这进一步推动了一种灵活的合成产乙酸细菌素的策略的发展。还描述了两种天然产物，即(,)-muricatacin和(,)-L-因子的简洁且无保护基的不对称全合成。
