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单配位烯丙基钯物种的动态行为：内配位作为烯丙基烷基化化学中的驱动力

Dynamic behaviour of monohaptoallylpalladium species: internal coordination as a driving force in allylic alkylation chemistry.

作者信息

Xie Lan-Gui, Bagutski Viktor, Audisio Davide, Wolf Larry M, Schmidts Volker, Hofmann Kathrin, Wirtz Cornelia, Thiel Walter, Thiele Christina M, Maulide Nuno

机构信息

University of Vienna , Institute of Organic Chemistry , Währinger Strasse 38 , 1090 Vienna , Austria . Email:

Technische Universität Darmstadt , Clemens Schöpf Institut für Organische Chemie und Biochemie , Alarich-Weiss-Str. 4 , 64287 Darmstadt , Germany . Email:

出版信息

Chem Sci. 2015 Oct 1;6(10):5734-5739. doi: 10.1039/c5sc01867f. Epub 2015 Jul 6.

DOI:10.1039/c5sc01867f
PMID:29910865
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5975841/
Abstract

Contemporary catalytic procedures involving alkylpalladium(ii) have enriched the arsenal of synthetic organic chemistry. Those transformations usually rely on internal coordination through "directing groups", carefully designed to maximize catalytic efficiency and regioselectivity. Herein, we report structural and reactivity studies of a series of internally coordinated monohaptoallylpalladium complexes. These species enable the direct spectroscopic observation and theoretical study of π-σ-π interconversion processes. They further display unusual dynamic behavior which should be of direct relevance to chemistries beyond catalytic allylic alkylation.

摘要

涉及烷基钯（II）的当代催化方法丰富了有机合成化学的手段。这些转化通常依赖于通过精心设计的“导向基团”进行的内配位，以最大限度地提高催化效率和区域选择性。在此，我们报告了一系列内配位单齿烯丙基钯配合物的结构和反应性研究。这些物种能够对π-σ-π相互转化过程进行直接的光谱观察和理论研究。它们还表现出不寻常的动态行为，这应该与催化烯丙基烷基化以外的化学直接相关。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/6cab92fca3e1/c5sc01867f-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/a086a3e7bdcb/c5sc01867f-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/412d09b01bd5/c5sc01867f-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/f4d06644226a/c5sc01867f-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/3baa6ef57c55/c5sc01867f-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/6cab92fca3e1/c5sc01867f-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/a086a3e7bdcb/c5sc01867f-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/96955c086922/c5sc01867f-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/ac1e7ad2ec82/c5sc01867f-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/504df022a654/c5sc01867f-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/baaaed9f3e00/c5sc01867f-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/95ccbc69bf7c/c5sc01867f-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/412d09b01bd5/c5sc01867f-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/f4d06644226a/c5sc01867f-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/3baa6ef57c55/c5sc01867f-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/166e/5975841/6cab92fca3e1/c5sc01867f-s6.jpg

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