Kenan, Caudill, Venable, and Murray Laboratories of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA.
Org Lett. 2012 Apr 20;14(8):2168-71. doi: 10.1021/ol3007259. Epub 2012 Apr 3.
The first enantioselective total synthesis of the proposed structure of aldingenin B is reported in 16 steps from known compounds. The stereochemistry at C5 and C6 were established by an asymmetric acetal aldol. Following a ring-closing metathesis, a selective, substrate-controlled hydrogen bond-mediated dihydroxylation provided control of the C2 and C3 stereocenters. Discrepancies in the spectroscopic data of the synthetic and natural material led to the conclusion that the structure of the natural sample was misassigned.
首次报道了 aldingenin B 的提议结构的对映选择性全合成，该合成从已知化合物出发经 16 步反应完成。C5 和 C6 的立体化学通过不对称缩醛醇醛反应建立。进行环化复分解反应后，选择性地、受底物控制的氢键介导的二羟基化反应控制了 C2 和 C3 立体中心。天然产物和合成产物的光谱数据存在差异，这导致了对天然样品结构的错误归属。
