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特屈儿-均二苯代乙烯与苯乙炔的加成反应

Tetryl-Tetrylene Addition to Phenylacetylene.

作者信息

Maudrich Jakob-Jonathan, Diab Fatima, Weiß Sebastian, Zweigart Magda, Eichele Klaus, Schubert Hartmut, Müller Robert, Kaupp Martin, Wesemann Lars

机构信息

Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.

Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.

出版信息

Chemistry. 2021 Mar 8;27(14):4691-4699. doi: 10.1002/chem.202005119. Epub 2021 Feb 4.

DOI:10.1002/chem.202005119
PMID:33332670
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7986144/
Abstract

Phenylacetylene adds [ArGeH -SnAr'], [ArGeH -PbAr'] and [Ar'SnH -PbAr*] at rt in a regioselective and stereoselective reaction. The highest reactivity was found for the stannylene, which reacts immediately upon addition of one equivalent of alkyne. However, the plumbylenes exhibit addition to the alkyne only in reaction with an excess of phenylacetylene. The product of the germylplumbylene addition reacts with a second equivalent of alkyne and the product of a CH-activation, a dimeric lead acetylide, were isolated. In the case of the stannylplumbylene the trans-addition product was characterized as the kinetically controlled product which isomerizes at rt to yield the cis-addition product, which is stabilized by an intramolecular Sn-H-Pb interaction. NMR chemical shifts of the olefins were investigated using two- and four-component relativistic DFT calculations, as spin-orbit effects can be large. Hydride abstraction was carried out by treating [Ar'SnPhC=CHGeH Ar*] with the trityl salt [Ph C][Al(OC{CF }) ] to yield a four membered ring cation.

摘要

苯乙炔在室温下以区域选择性和立体选择性反应与[ArGeH -SnAr']、[ArGeH -PbAr']和[Ar'SnH -PbAr*]发生加成反应。发现亚锡烯的反应活性最高，加入一当量炔烃后立即反应。然而，亚铅烯仅在与过量苯乙炔反应时才与炔烃发生加成反应。亚锗基亚铅烯加成反应的产物与第二当量的炔烃反应，并分离出CH活化产物——二聚乙炔铅。对于亚锡基亚铅烯，反式加成产物被表征为动力学控制产物，其在室温下异构化生成顺式加成产物，该产物通过分子内Sn-H-Pb相互作用得以稳定。由于自旋轨道效应可能很大，因此使用二分量和四分量相对论密度泛函理论计算研究了烯烃的核磁共振化学位移。用三苯甲基盐[Ph C][Al(OC{CF }) ]处理[Ar'SnPhC=CHGeH Ar*]进行氢化物提取，得到一个四元环阳离子。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d6/7986144/8af5e0aed3f4/CHEM-27-4691-g004.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d6/7986144/58954a2c40c3/CHEM-27-4691-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/08d6/7986144/f2a3918a50b8/CHEM-27-4691-g010.jpg
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