P(NMe)-介导的 - 醌亚甲基螺环丙烷基化反应：螺环丙烷-环己二烯酮的非对映选择性合成。
P(NMe)-Mediated Umpolung Spirocyclopropanation Reaction of -Quinone Methides: Diastereoselective Synthesis of Spirocyclopropane-Cyclohexadienones.
机构信息
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Research & Development Center for Natural Products, and School of Chemical Science and Technology, Yunnan University, No. 2 Cuihu North Road, Kunming 650091, China.
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 Tianshui Nanlu, Lanzhou 730000, China.
出版信息
Org Lett. 2020 Nov 6;22(21):8376-8381. doi: 10.1021/acs.orglett.0c02998. Epub 2020 Oct 12.
An unprecedented umpolung spirocyclopropanation reaction of -quinone methides and α-keto carbonyls is described. Our umpolung strategy based on 1,6-conjugate addition and intramolecular nucleophilic substitution offers a new method for effective access to a series of highly functionalized spirocyclohexadienonyl cyclopropanes having two vicinal quaternary carbons in ≤98% yield and >20:1 dr. Significantly, cyclic and acyclic topological structures of α-keto carbonyls as 1,1-dipole one-carbon synthons have a distinct influence on the stereochemistry of products, showing a reversal of diastereoselectivity in this P(NMe)-mediated umpolung spirocyclopropanation.
我们描述了一种前所未有的 -醌甲川和α-酮羰基的反极性螺环丙烷基化反应。我们基于 1,6-共轭加成和分子内亲核取代的反极性策略为有效构建一系列高度官能化的螺环环己二烯基环丙烷提供了一种新方法，这些环丙烷具有两个相邻的季碳原子，产率高达 98%，dr 值大于 20:1。重要的是，α-酮羰基作为 1,1-偶极子一碳合成子的环状和非环状拓扑结构对产物的立体化学有明显的影响，在这种 P(NMe)介导的反极性螺环丙烷基化反应中表现出对映选择性的反转。
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