芳香聚酮 NFAT-133 的合成与立体化学修订。
Synthesis and Stereochemical Revision of the Aromatic Polyketide NFAT-133.
机构信息
Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural Science , Tohoku University , 468-1 Aramaki-Aza-Aoba, Aoba-ku, Sendai 980-0845 , Japan.
Research and Analytical Center for Giant Molecules, Graduate School of Science , Tohoku University , Sendai 980-8578 , Japan.
出版信息
J Nat Prod. 2019 Jul 26;82(7):1791-1796. doi: 10.1021/acs.jnatprod.8b01063. Epub 2019 Jul 3.
NFAT-133, isolated from sp., is an immunosuppressive, antidiabetic, and antitrypanosomal aromatic polyketide with three contiguous stereocenters. The first enantioselective total synthesis of the proposed structure of NFAT-133 [(10,11,12)-] and its C10 epimer [(10,11,12)-] was achieved from a known aromatic ester () by a 10-step sequence that featured chiral auxiliary-directed asymmetric alkylation and the Evans asymmetric aldol reaction as the chirality-inducing steps. The H and C NMR data as well as the specific rotation value of natural NFAT-133 were not identical to those of the proposed structure, but were in good agreement with those of its C10 epimer. This led us to conclude that the absolute configuration of NFAT-133 should be revised to 10, 11, and 12.
NFAT-133 是从 sp. 中分离得到的一种具有三个连续手性中心的免疫抑制、抗糖尿病和抗锥虫芳香聚酮。通过 10 步反应序列，包括手性辅助导向的不对称烷基化和 Evans 不对称羟醛反应作为手性诱导步骤，从已知芳香酯 () 实现了 NFAT-133[(10,11,12)-]及其 C10 差向异构体[(10,11,12)-]的首次对映选择性全合成。天然 NFAT-133 的 H 和 C NMR 数据以及比旋光度与所提出的结构不一致，但与 C10 差向异构体吻合较好。这使我们得出结论，NFAT-133 的绝对构型应修订为 10、11 和 12。
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