钯催化双(环戊二烯基)二芳基钛与末端炔的交叉偶联反应

Reactions Pub Date : 2023-10-19 DOI:10.3390/reactions4040037
Yuki Murata, Yuya Nishi, Mio Matsumura, Shuji Yasuike
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引用次数: 0

摘要

有机钛化合物在各种反应中都有应用,包括碳-碳键的形成和氧化。虽然钛(IV)化合物已用于各种应用,但双(环戊二烯基)二芳基钛在交叉偶联反应中的潜力仍未被探索。本文主要研究了涉及末端炔和有机钛化合物的sonogashura型交叉偶联反应。以二氯化二茂钛和碘化芳基衍生的锂为中间体合成了二芳基二茂钛。在开烧瓶条件下,二苯二茂钛与乙基苯在DMF中以20 mol% Pd(OAc)2存在的条件下反应,偶联产物的产率达到了99%。在标准条件下,各种二芳基二茂钛和炔烃均可得到相应的交偶联产物,产率均为中高。值得注意的是,sonogashira型烷基化反应在温和的条件下进行,包括开瓶条件,并且不需要碱。此外,这种交叉偶联是原子经济的,并且涉及二芳基二茂钛的两个芳基的积极参与。值得注意的是,这项研究提出了sonogashura型交叉偶联的第一个例子,使用钛化合物作为伪卤化物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes
Organotitanium compounds find application in diverse reactions, including carbon–carbon bond formation and oxidation. While titanium (IV) compounds have been used in various applications, the potential of bis(cyclopentadienyl)diaryltitanium in cross-coupling reactions remains unexplored. This study focuses on Sonogashira-type cross-coupling reactions involving terminal alkynes and organotitanium compounds. Diaryltitanocenes were synthesized using titanocene dichloride with lithium intermediates derived from aryl iodide. Under open-flask conditions, reactions of diphenyltitanocenes with ethynylbenzene in the presence of 20 mol% Pd(OAc)2 in DMF produced coupling products in a remarkable 99% yield. Various diaryltitanocenes and alkynes under standard conditions yielded corresponding cross-coupling products with moderate to good yields. Notably, the Sonogashira-type alkynylation proceeds under mild conditions, including open-flask conditions, and without the need for a base. Furthermore, this cross-coupling is atom-economical and involves the active participation of both aryl groups of the diaryltitanocene. Remarkably, this study presents the first example of a Sonogashira-type cross-coupling using titanium compounds as pseudo-halides.
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CiteScore
2.70
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