Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Alicante, Apdo. 99, E-03080 Alicante, Spain.
Org Biomol Chem. 2020 Feb 19;18(7):1279-1336. doi: 10.1039/c9ob02597a.
Enantio- and diastereodivergent routes to marine-origin natural products with different sizes of cyclic ethers and lactones have been used in order to assign stereochemical features. Kainoid amino acids such as isodomoic acids have been synthesized using diastereodivergent routes. The bis(indole) alkaloid dragmacidin F has been prepared by enantiodivergent strategies as well as furanoterpenes and the tetracyclic agelastatin A. Natural products containing five-membered lactones like quercus lactones, muricatacins, goniofufuranones, methylenolactocins and frenolicin B have been synthesized using stereodivergent routes. Macrolides are very abundant lactones and have been mainly prepared from the corresponding seco-acids by lactonization, such as lasiodiplodin, zaeralanes, macrosphelides and haloprins, or by ring-closing metathesis, such as aspercyclides, microcarpalides, macrolides FD-891 and 892, and tetradic-5-en-9-olides. Other natural products including cyclic ethers (such as sesamin, asarinin, acetogenins, centrolobines and nabilones), alcohols (such as sulcatol), esters (such as methyl jasmonates), polycyclic precursors of fredericamycin, amino alcohols (such as ambroxol and sphingosines), isoprostanes, isofurans, polyketide precursors of anachelins, brevicomins, gummiferol, shikimic acid and the related compounds, and the pheromone disparlure have been synthesized stereodivergently. Heterocyclic systems such as epoxides, theobroxides and bromoxones, oxetan-3-ones, 5- to 8-membered cyclic ethers, azetidones, γ-lactams, oxazolidinones, bis(oxazolines), dihydropyridoisoindolines and octahydroisoquinolines have been prepared following stereodivergent routes. Stereodivergent routes to unnatural compounds such as alkenes, dienes, allenes, cyclopropanes, alcohols, aldols, amines, amino alcohols, β-amino acids, carboxylic acids, lactones, nitriles and α-amino nitriles have been considered as well.
为了确定立体化学特征，已经使用了具有不同大小的环醚和内酯的海洋源天然产物的对映体和非对映体发散途径。已经使用非对映体发散途径合成了 kainoid 氨基酸，如异同型酸。双（吲哚）生物碱 dragmacidin F 也通过对映体发散策略以及呋喃萜烯和四环 agelastatin A 进行了制备。使用立体发散途径合成了含有五元内酯的天然产物，如栎属内酯、muricatacins、goniofufuranones、methyleneolactocins 和 frenolicin B。大环内酯是非常丰富的内酯，主要通过内酯化从相应的 sec-酸制备，如 lasiodiplodin、zaeralanes、macrosphelides 和 haloprins，或通过闭环复分解反应，如 aspercyclides、microcarpalides、macrolides FD-891 和 892 以及四元-5-烯-9-内酯。其他天然产物包括环醚（如 sesamin、asarinin、acetogenins、centrolobines 和 nabilones）、醇（如 sulcatol）、酯（如甲基茉莉酸盐）、fredericamycin 的多环前体、氨基醇（如 ambroxol 和鞘氨醇）、异前列烷、异呋喃、anachelins、brevicomins、gummiferol、shikimic acid 和相关化合物的聚酮前体以及信息素 disparlure 也通过立体发散进行了合成。立体发散途径还制备了杂环系统，如环氧化物、theobroxides 和 bromoxones、氧杂环丁烷-3-酮、5-8 元环醚、氮杂环丁烷、γ-内酰胺、恶唑烷酮、双（恶唑啉）、二氢吡啶并异吲哚啉和八氢异喹啉。还考虑了非天然化合物的立体发散途径，如烯烃、二烯、炔烃、环丙烷、醇、羟醛、胺、氨基醇、β-氨基酸、羧酸、内酯、腈和α-氨基腈。
