Construction of vicinal 4°/3°-carbons via reductive Cope rearrangement.

Construction of vicinal 4°/3°-carbons via reductive Cope rearrangement.
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DOI:
10.1039/d1sc06307c
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发表时间:
2022-02-16
期刊:
影响因子:
8.4
通讯作者:
Grenning AJ
Grenning AJ
中科院分区:
化学1区
文献类型:
--
作者:
Sobie KM;Albritton M;Yang Y;Alves MM;Roitberg A;Grenning AJ

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本文报道了通过还原性科普重排构建邻位4°/3°碳的策略。已经设计出的底物表现出科普重排动力学势垒为1.23 kcal mol−1,具有等能重排能力(ΔG ≥ 0)。这些流动的/形状变化的分子可以通过化学选择性还原被向前驱动为有用的多官能化结构单元。本文报道了通过还原性科普重排构建邻位4°/3°碳的策略。
Herein reported is a strategy for constructing vicinal 4°/3° carbons via reductive Cope rearrangement. Substrates have been designed which exhibit Cope rearrangement kinetic barriers of ∼23 kcal mol−1 with isoenergetic favorability (ΔG ∼ 0). These fluxional/shape-shifting molecules can be driven forward by chemoselective reduction to useful polyfunctionalized building blocks. Herein reported is a strategy for constructing vicinal 4°/3° carbons via reductive Cope rearrangement.
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