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百万分之几的钌催化剂能够促进末端烯烃的选择性链行走反应。

Parts-per-million of ruthenium catalyze the selective chain-walking reaction of terminal alkenes.

机构信息

Instituto de Tecnología Química (UPV-CSIC), Universidad Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.

Departament de Química Analítica, Universitat de Valencia, Dr Moliner, 50, 46100, Burjassot, Valencia, Spain.

出版信息

Nat Commun. 2022 May 20;13(1):2831. doi: 10.1038/s41467-022-30320-9.

DOI:10.1038/s41467-022-30320-9
PMID:35595741
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9123009/
Abstract

The chain-walking of terminal alkenes (also called migration or isomerization reaction) is currently carried out in industry with unselective and relatively costly processes, to give mixtures of alkenes with significant amounts of oligomerized, branched and reduced by-products. Here, it is shown that part-per-million amounts of a variety of commercially available and in-house made ruthenium compounds, supported or not, transform into an extremely active catalyst for the regioselective migration of terminal alkenes to internal positions, with yields and selectivity up to >99% and without any solvent, ligand, additive or protecting atmosphere required, but only heating at temperatures >150 °C. The resulting internal alkene can be prepared in kilogram quantities, ready to be used in nine different organic reactions without any further treatment.

摘要

末端烯烃的链转移(也称为迁移或异构化反应)目前在工业上采用非选择性且相对昂贵的方法进行,以得到具有大量齐聚物、支化和还原副产物的烯烃混合物。在这里,研究表明,ppm 数量级的各种市售和内部制备的钌化合物(负载或未负载)转化为末端烯烃区域选择性迁移到内部位置的极其活跃的催化剂,产率和选择性高达>99%,且不需要任何溶剂、配体、添加剂或保护气氛,但只需在>150°C 的温度下加热。得到的内烯烃可以以千克级的量制备,准备在九种不同的有机反应中使用,无需进一步处理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/3acf072dcc98/41467_2022_30320_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/05fadca19008/41467_2022_30320_Fig1_HTML.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/e1d333704053/41467_2022_30320_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/49a476693c44/41467_2022_30320_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/26e76dba9b1e/41467_2022_30320_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/3acf072dcc98/41467_2022_30320_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/05fadca19008/41467_2022_30320_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/9f8ae70b1a38/41467_2022_30320_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/e1d333704053/41467_2022_30320_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/49a476693c44/41467_2022_30320_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/26e76dba9b1e/41467_2022_30320_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/49ae/9123009/3acf072dcc98/41467_2022_30320_Fig6_HTML.jpg

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