Thommen Christophe, Neuburger Markus, Gademann Karl
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.
Department of Chemistry, University of Basel, St-Johanns-Ring 19, 4056, Basel, Switzerland.
Chemistry. 2017 Jan 1;23(1):120-127. doi: 10.1002/chem.201603932. Epub 2016 Nov 29.
A divergent synthesis of 10 icetexane natural products based on a proposed biogenetic cationic ring expansion of a reduced carnosic acid derivative is described. Of these icetexanes, (+)-salvicanol, (-)-cyclocoulterone, (-)-coulterone, (-)-obtusinone D, and (-)-obtusinone E have been synthesized for the first time. In addition, the hypothesis for the non-enzymatic biogenesis of benzo[1,3]dioxole natural products has been experimentally investigated. Additional experimental evidence for the abiotic formation of the methylenedioxy unit is provided, as photolysis of the quinone (+)-komaroviquinone resulted in the formation of the [1,3]dioxole-containing natural product (-)-cyclocoulterone and (+)-komarovispirone.
本文描述了基于还原型鼠尾草酸衍生物的一种假定生物合成阳离子环扩展反应，对10种icetexane天然产物进行的发散性合成。在这些icetexane天然产物中，(+)- salvicanol、(-)-环古豆素、(-)-古豆素、(-)- obtusinone D和(-)- obtusinone E均为首次合成。此外，还通过实验研究了苯并[1,3]二氧杂环戊烯天然产物非酶生物合成的假说。提供了亚甲基二氧基单元非生物形成的额外实验证据，因为醌(+)-柯玛罗醌的光解导致了含[1,3]二氧杂环戊烯的天然产物(-)-环古豆素和(+)-柯玛罗螺酮的形成。
