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5-（炔基）二苯并噻吩鎓盐的反应活性：二炔、乙烯基砜和菲的合成

Reactivity of 5-(Alkynyl)dibenzothiophenium Salts: Synthesis of Diynes, Vinyl Sulfones, and Phenanthrenes.

作者信息

Kafuta Kevin, Rugen Christian J, Heilmann Tobias, Liu Tianshu, Golz Christopher, Alcarazo Manuel

机构信息

Institut für Organische und Biomolekulare Chemie Georg-August-Universität Göttingen Tammannstr 2 37077 Göttingen Germany.

出版信息

European J Org Chem. 2021 Aug 6;2021(29):4038-4048. doi: 10.1002/ejoc.202100323. Epub 2021 May 5.

DOI:10.1002/ejoc.202100323
PMID:34588919
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8453815/
Abstract

The reactivity of 5-(alkynyl)dibenzothiophenium salts is explored in the presence of different nucleophiles, dienes, and under photochemical conditions. Reaction with lithium acetylides affords diynes in moderate yields; while depending on the substitution pattern, the reaction with sulfinates delivers either the alkyne transfer products, alkynyl sulfones, or β-(sulfonium) vinyl sulfones through addition to the C-C triple bond. Similar behavior is observed when tosylamines are used as nucleophiles. Salts of general formula also react with dienes to render the corresponding Diels-Alder cycloadducts. The vinyl sulfonium salts obtained by these routes further react with nucleophiles through a Michael addition, dibenzothiophene elimination sequence. Alternatively, they also engage in photoinduced radical cyclizations to produce substituted phenanthrenes. Attempts to use this specific addition/radical cyclization sequence for the construction of the 6,7-dehydroaporphine skeleton present in several families of alkaloids are also described.

摘要

在不同亲核试剂、二烯存在的情况下以及光化学条件下，对5-（炔基）二苯并噻吩盐的反应活性进行了探索。与乙炔锂反应可中等产率地得到二炔；而根据取代模式，与亚磺酸盐反应时，通过加成到碳 - 碳三键上，可得到炔基转移产物、炔基砜或β-（锍）乙烯基砜。当使用对甲苯磺酰胺作为亲核试剂时，也观察到类似的行为。通式盐也与二烯反应生成相应的狄尔斯 - 阿尔德环加成物。通过这些途径得到的乙烯基锍盐进一步通过迈克尔加成、二苯并噻吩消除序列与亲核试剂反应。或者，它们也参与光诱导自由基环化反应以生成取代菲。还描述了尝试使用这种特定的加成/自由基环化序列来构建存在于几个生物碱家族中的6,7 - 脱氢阿朴菲骨架。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/05bdb02fa1cf/EJOC-2021-4038-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/9974ee9260e9/EJOC-2021-4038-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/1fd59db9db46/EJOC-2021-4038-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/63632071ca61/EJOC-2021-4038-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/8df1863ed233/EJOC-2021-4038-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/5e97c67d7f51/EJOC-2021-4038-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/8f4281b67c93/EJOC-2021-4038-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/f7c8785ff714/EJOC-2021-4038-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/aa3005c21ec1/EJOC-2021-4038-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/05bdb02fa1cf/EJOC-2021-4038-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/9974ee9260e9/EJOC-2021-4038-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/1fd59db9db46/EJOC-2021-4038-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/63632071ca61/EJOC-2021-4038-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/8df1863ed233/EJOC-2021-4038-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/5e97c67d7f51/EJOC-2021-4038-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/8f4281b67c93/EJOC-2021-4038-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/f7c8785ff714/EJOC-2021-4038-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/aa3005c21ec1/EJOC-2021-4038-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f432/8453815/05bdb02fa1cf/EJOC-2021-4038-g002.jpg

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