Center for New Directions in Organic Synthesis, Department of Chemistry , Hanyang University , 222 Wangshimni-ro , Seongdong-gu, Seoul 04763 , Korea.
Org Lett. 2018 Nov 16;20(22):7312-7316. doi: 10.1021/acs.orglett.8b03250. Epub 2018 Nov 7.
An asymmetric formal total synthesis of (+)-aplykurodinone-1 was achieved using a route, in which hydrogen bonding serves as a stereochemical control element governing the π-facial selectivity of intramolecular Diels-Alder (IMDA) reaction of an enone tethered 2-pyrone. In the IMDA process, the configuration at a stereogenic, hydroxyl bearing an α-carbon in the enone dienophile is conveyed in a highly effective manner through intramolecular hydrogen bonding with the enone carbonyl oxygen. The tricyclic lactone, generated in this process, was successfully converted to a late stage intermediate in Danishefsky's synthesis of aplykurodinone-1.
（+）-阿朴拉酮-1 的不对称全合成采用一种路线实现，其中氢键作为立体化学控制元件，控制与烯酮二烯亲合物连接的 2-吡喃酮的分子内 Diels-Alder（IMDA）反应的π-面选择性。在 IMDA 过程中，烯酮二烯亲合物中带有立体中心的α-碳上的羟基的构型通过与烯酮羰基氧的分子内氢键以高效的方式传递。在此过程中生成的三环内酯成功转化为 Danishefsky 合成阿朴拉酮-1 的后期中间体。
