- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Photo‐Organocatalytic Enantioselective Radical Cascade Enabled by Single‐Electron Transfer Activation of Allenes
摘要： Allenes are commonly used in metal-mediated transformations, cycloaddition reactions, and radical processes. However, their activation by single-electron transfer (SET) is largely underexplored. Herein, we report a visible light-driven enantioselective organocatalytic process that uses the excited-state reactivity of chiral iminium ions to activate allenes by SET oxidation. The ensuing allene cation radicals participate in stereocontrolled cascade reactions to deliver bicyclic scaffolds with good enantioselectivity and exquisite diastereoselectivity. Density Functional Theory (DFT) calculations support a mechanism that combines the peculiar chemistry of allene radical cations with polar reactivity.
关键词： photochemistry,cascade process,allene,enantioselective organocatalysis,radical chemistry
更新于2025-09-19 17:13:59
-
Rapid syntheses of (?)-FR901483 and (+)-TAN1251C enabled by complexity-generating photocatalytic olefin hydroaminoalkylation
摘要： We report a common strategy to facilitate the syntheses of the polycyclic alkaloids (?)-FR901483 (1) and (+)-TAN1251C (2). A divergent synthetic strategy provides access both natural products through a pivotal spirolactam intermediate (3), which can be accessed on a gram-scale. A photocatalytic olefin hydroaminoalkylation brings together three readily available building blocks and forges the majority of the carbon framework present in 1 and 2 in a single operation, leading to concise total syntheses. The complexity-generating photocatalytic process also provides direct access to novel non-racemic spirolactam scaffolds that are likely to be of interest to early-stage drug discovery programs.
关键词： medicinal chemistry,natural product synthesis,amine synthesis,photoredox chemistry,radical chemistry
更新于2025-09-12 10:27:22