Boyce Thompson Institute and Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA.
Org Lett. 2011 Nov 4;13(21):5900-3. doi: 10.1021/ol202541b. Epub 2011 Oct 12.
A cross metathesis (CM)-based synthesis of the caeliferins, a family of sulfooxy fatty acids that elicit plant immune responses, is reported. Unexpectedly, detailed NMR spectroscopic and mass spectrometric analyses of CM reaction mixtures revealed extensive isomerization and homologation of starting materials and products. It is shown that the degree of isomerization and homologation in CM strongly correlates with substrate chain length and lipophilicity. Side-product suppression requires appropriate catalyst selection and use of 1,4-benzoquinone as a hydride scavenger.
报告了基于交叉复分解（CM）的 caeliferin 的合成，caeliferin 是一类能够引发植物免疫反应的磺酸氧基脂肪酸。出乎意料的是，对 CM 反应混合物的详细 NMR 光谱和质谱分析显示了起始材料和产物的广泛异构化和同系化。结果表明，CM 中的异构化和同系化程度与底物链长和疏水性密切相关。需要选择合适的催化剂，并使用 1,4-苯醌作为氢化物清除剂来抑制副产物。
