Suzuki Junya, Miyano Natsumi, Yashiro Shunpei, Umezawa Taiki, Matsuda Fuyuhiko
Graduate School of Environmental Science, Hokkaido University, N10 W5, Sapporo 060-0810, Japan.
Org Biomol Chem. 2017 Aug 9;15(31):6557-6566. doi: 10.1039/c7ob01427a.
A 3,4-disubstituted pyrrolidine ring was effectively cyclized through SmI-mediated reductive coupling between allyl chloride and an α,β-unsaturated ester, although little has been reported about SmI-promoted C-C bond formation of an allyl chloride with an α,β-unsaturated ester. Selection of either the 3,4-cis- or 3,4-trans-selective cyclization can be accomplished simply by changing the additives from NiI to HMPA during reductive cyclization conducted in HO-THF. Total synthesis of (-)-kainic acid and (+)-allo-kainic acid, which are pyrrolidine alkaloids used in neuroscience and neuropharmacology as useful molecular probes, was successfully achieved by using the stereo-complementary ring closure reactions promoted by SmI for the construction of the 2,3,4-trisubsituted pyrrolidine scaffold of kainoids.
通过二碘化钐介导的烯丙基氯与α,β-不饱和酯之间的还原偶联反应，3,4-二取代吡咯烷环能够有效地环化，尽管关于二碘化钐促进烯丙基氯与α,β-不饱和酯形成碳-碳键的报道很少。在HO-THF中进行还原环化时，只需将添加剂从碘化镍改为六甲基磷酰胺，即可实现3,4-顺式或3,4-反式选择性环化。（-）-红藻氨酸和（+）-别红藻氨酸是用于神经科学和神经药理学的有用分子探针的吡咯烷生物碱，通过使用二碘化钐促进的立体互补闭环反应成功实现了它们的全合成，用于构建红藻氨酸类化合物的2,3,4-三取代吡咯烷骨架。
