Designing an Apparently Orbital‐Symmetry‐Forbidden [3s,5s]‐Sigmatropic Shift through Transition‐State Complexation and Stereoelectronic Effects
Designing an Apparently Orbital‐Symmetry‐Forbidden [3s,5s]‐Sigmatropic Shift through Transition‐State Complexation and Stereoelectronic Effects
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设计明显的轨道 — 对称性 — 禁止的 [3s,5s] — 通过跃迁的 Sigmatropic 转变 — 状态络合和立体电子效应
DOI：
10.1002/anie.202300288
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Tantillo, Dean J.
中科院分区：
文献类型：
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作者：
Ahmed, Yusef G.;Tantillo, Dean J.
[3s，5s]‐信号移是轨道对称禁止周环反应被允许的[3s，3s]‐信号移所取代的一个例子。密度泛函理论计算表明，具有战略性位置的取代基参与关键立体电子效应的PdII -复杂体系可以选择[3s，5s]过程，从而优于轨道-对称-允许的[3s，3s] -和[3s，5a] -位移。
The [3s,5s]‐sigmatropic shift is an example of an orbital‐symmetry forbidden pericyclic reaction that is outcompeted by the allowed [3s,3s]‐sigmatropic shift. Density functional theory calculations are used to show that PdII‐complexed systems with strategically placed substituents engaging in key stereoelectronic effects can select for the [3s,5s] process, thereby outcompeting both orbital‐symmetry‐allowed [3s,3s]‐ and [3s,5a]‐shifts.