UNIROUEN, INSA Rouen, CNRS, COBRA, Normandie Univ, 76000, Rouen, France.
CNRS, Laboratoire de Chimie Théorique, LCT UMR7616, Sorbonne Université, 75005, Paris, France.
Chemistry. 2019 Oct 28;25(60):13688-13693. doi: 10.1002/chem.201903455. Epub 2019 Sep 30.
3-Nitroindoles are easily reacted with highly substituted γ-allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3-nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α-regioisomers exclusively. DFT computations shed light on this multi-step reaction mechanism and on the selectivities observed in the sequence.
3-硝基吲哚在市售膦配体催化剂的存在下很容易与高取代的γ-allenolates 反应。例如，首次将生物分子（如氨基酸和脱氧胆酸）衍生的 allenolates 与 3-硝基吲哚结合。相应的去芳构化（3+2）三环环加成产物作为 α-区域异构体被专一得到。DFT 计算阐明了该多步反应机理以及该序列中观察到的选择性。
