Dipartimento di Scienze del Farmaco, Università del Piemonte Orientale, L.go Donegani 2, 28100, Novara, Italy.
Dipartimento di Farmacia, Università di Napoli Federico II, Via Montesano 49, 80131, Napoli, Italy.
Angew Chem Int Ed Engl. 2017 Jun 26;56(27):7935-7938. doi: 10.1002/anie.201703455. Epub 2017 Jun 5.
An approach to biogenetically overlooked areas of the isoprenoid chemical space is presented. This strategy is based on the generation of a cationic center in functionalized polyolefins by Lewis acid activation of a carbonyl group, rather than by electrophilic attack at a double bond. Starting from the monocyclic humulane trienone zerumbone, polycyclic sesquiterpenoid skeletons which are either not reported as natural products or biogenetically enigmatic in terms of the isoprenoid rule, were obtained by modulating the Lewis acid catalyst. In the course of these studies, the surprising formation of a strained E-cyclooctene motif was observed in a cyclization reaction.
本文提出了一种生物起源被忽视的类异戊二烯化学空间的研究方法。该策略基于通过路易斯酸激活羰基而不是通过双键的亲电攻击在功能化聚烯烃中生成正电荷中心。从单环葎草烯三烯酮、缬草酮出发，通过调节路易斯酸催化剂，得到了未报道为天然产物或在类异戊二烯规则方面具有生物起源之谜的多环倍半萜骨架。在这些研究过程中，在环化反应中观察到了一个应变的 E-环辛烯基序的惊人形成。
