New ventures in the chemistry of avermectins
New ventures in the chemistry of avermectins
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DOI：
10.1016/j.bmc.2008.12.069
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发表时间：
2009-06-15
影响因子：
3.5
通讯作者：
Tobler, Hans
中科院分区：
文献类型：
--
作者：
Pitterna, Thomas;Cassayre, Jerome;Tobler, Hans
综述了近年来国内外对具有极高杀虫杀螨活性的阿维菌素衍生物的研究进展。这些化合物由市售阿维菌素（阿维菌素B1）1制备。对于合成，许多新的条目已经打开，利用现代合成方法，并将其应用于第一次，阿维菌素的化学。几种类型的阿维菌素衍生物可被视为该领域的关键创新。特别是4“-脱氧-4”-（S）-氨基阿维菌素3，4“-O-烷氧基烷基阿维菌素单糖5，4”-脱氧-4“-C-取代的4”-氨基阿维菌素6和2“-取代的阿维菌素7。4“-脱氧-4”-（S）-氨基阿维菌素3通过Staudinger和Aza-Wittig反应得到。以阿维菌素5-O-保护基单糖为原料，经烷氧基烷基化反应，制备了4 '-O-烷氧基烷基阿维菌素5。为了合成4“-脱氧-4”-C-取代的4“-氨基阿维菌素6，使用了几种方法来构建完全取代的4”-碳中心，例如改进的Strecker合成，将有机金属化合物添加到4“-亚磺亚胺和改进的Ugi方法。为了制备2“-取代的阿维菌素7，5-O-保护的阿维菌素单糖与碳水化合物结构单元偶联。另一种合成方法涉及迄今未知的4“-氧代-阿维菌素的烯醇醚化学和铜酸盐与阿维菌素2”，3“-烯-4”-酮的共轭加成。此外，还合成了许多其他高效衍生物。实例是4“-O-氨基阿维菌素8，以及由分子内铑催化酰胺化和卡宾插入产生的产物。一个自由基环化导致了一个有趣的阿维菌素骨架重排。许多新的阿维菌素对昆虫和螨的活性超过阿维菌素1。(C)2009爱思唯尔有限公司保留所有权利。
An overview is given on recent work towards new avermectin derivatives of extremely high insecticidal and acaricidal activity. These compounds were prepared from commercially available abamectin (avermectin B1) 1. For the synthesis, many novel entries have been opened up, making use of modern synthetic methods and applying them, for the first time, to the chemistry of avermectins. Several types of avermectin derivatives can be regarded as key innovations in the field. These are, in particular, 4 ''-deoxy-4 ''-(S)-amino avermectins 3, 4'-O-alkoxyalkyl avermectin monosaccharides 5, 4 ''-deoxy-4 ''-C-substituted 4 ''-amino avermectins 6 and 2 ''-substituted avermectins 7. 4 ''-Deoxy-4 ''-(S)-amino avermectins 3 were obtained by the consecutive application of the Staudinger and Aza-Wittig reaction. 4'-O-Alkoxyalkyl avermectin monosaccharides 5 were prepared by alkoxyalkylation of 5-O-protected avermectin monosaccharide. For the synthesis of 4 ''-deoxy-4 ''-C-substituted 4 ''-amino avermectins 6, several methods were used to construct the fully substituted 4 ''-carbon centre, such as a modified Strecker synthesis, the addition of organometallics to a 4 ''-sulfinimine and a modified Ugi approach. In order to prepare 2 ''-substituted avermectins 7, 5-O-protected avermectin monosaccharide was coupled with carbohydrate building blocks. An alternative synthesis involved the hitherto unknown enol ether chemistry of 4 ''-oxo-avermectin and the conjugate addition of a cuprate to an avermectin 2 '',3 ''-en-4 ''-one. In addition, a number of other highly potent derivatives were synthesised. Examples are 4 ''-O-amino avermectins 8, as well as products arising from intramolecular rhodium catalysed amidations and carbene insertions. A radical cyclisation led to an intriguing rearrangement of the avermectin skeleton. Many of the new avermectins surpassed the activity of abamectin 1 against insects and mites. (C) 2009 Elsevier Ltd. All rights reserved.