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1-磷杂-2-氮杂降冰片烯的还原重排

Reductive Rearrangement of a 1-Phospha-2-azanorbornene.

作者信息

Wonneberger Peter, König Nils, Sárosi Menyhárt B, Hey-Hawkins Evamarie

机构信息

Leipzig University, Faculty of Chemistry and Mineralogy, Institute of Inorganic Chemistry, Johannisallee 29, 04103, Leipzig, Germany.

出版信息

Chemistry. 2021 May 20;27(29):7847-7852. doi: 10.1002/chem.202100898. Epub 2021 May 3.

DOI:10.1002/chem.202100898
PMID:33780580
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8251630/
Abstract

The reduction of the 1-phospha-2-azanorbornene derivate endo-1 with lithium aluminium hydride leads to an unprecedented 1-phosphabicyclo[3.2.1]octa-2,5-diene, while a phospholide anion is formed with lithium. The latter can be protonated resulting in formation of an unusual 2H-phosphole dimer. Furthermore, 3H-phospholes, previously assumed to have no synthetic relevance as intermediates, were proposed to act as dienophile in the dimerisation of 3,4-dimethyl-1-phenylphosphole at elevated temperatures based on theoretical calculations.

摘要

用氢化铝锂还原1-磷杂-2-氮杂降冰片烯衍生物内型-1会生成一种前所未有的1-磷杂双环[3.2.1]辛-2,5-二烯，而与锂反应则会形成磷叶立德阴离子。后者可以质子化，从而形成一种不寻常的2H-磷杂环戊二烯二聚体。此外，基于理论计算，之前认为没有合成相关性的中间体3H-磷杂环戊二烯，在高温下被认为在3,4-二甲基-1-苯基磷杂环戊二烯的二聚反应中作为亲双烯体起作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/662296b4696c/CHEM-27-7847-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/8f5dee2b6d2d/CHEM-27-7847-g003.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/070e5c68df46/CHEM-27-7847-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/f03ea27fd816/CHEM-27-7847-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/68be2f88ab59/CHEM-27-7847-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/b3caf8d549bd/CHEM-27-7847-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/17f82695d956/CHEM-27-7847-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/f0dc8ade0adb/CHEM-27-7847-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/a0a6d2a6ea21/CHEM-27-7847-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/662296b4696c/CHEM-27-7847-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/8f5dee2b6d2d/CHEM-27-7847-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/f91e72278df2/CHEM-27-7847-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/a6a40bf5a458/CHEM-27-7847-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/be76815a6bb9/CHEM-27-7847-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/070e5c68df46/CHEM-27-7847-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/f03ea27fd816/CHEM-27-7847-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/68be2f88ab59/CHEM-27-7847-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/b3caf8d549bd/CHEM-27-7847-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/17f82695d956/CHEM-27-7847-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/f0dc8ade0adb/CHEM-27-7847-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/a0a6d2a6ea21/CHEM-27-7847-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f19/8251630/662296b4696c/CHEM-27-7847-g011.jpg

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