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...
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| Format: | Article |
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MDPI AG
2023-10-01
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| Series: | Reactions |
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| Online Access: | https://www.mdpi.com/2624-781X/4/4/37 |
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| author | Yuki Murata Yuya Nishi Mio Matsumura Shuji Yasuike |
| author_facet | Yuki Murata Yuya Nishi Mio Matsumura Shuji Yasuike |
| author_sort | Yuki Murata |
| collection | DOAJ |
| description | 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)<sub>2</sub> 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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| institution | Directory Open Access Journal |
| issn | 2624-781X |
| language | English |
| last_indexed | 2024-03-08T20:25:33Z |
| publishDate | 2023-10-01 |
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| spelling | doaj.art-efa2442284e9437cb13ed446a451ee6c2023-12-22T14:38:15ZengMDPI AGReactions2624-781X2023-10-014465766610.3390/reactions4040037Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal AlkynesYuki Murata0Yuya Nishi1Mio Matsumura2Shuji Yasuike3School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, JapanSchool of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, JapanSchool of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, JapanSchool of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, JapanOrganotitanium 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)<sub>2</sub> 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.https://www.mdpi.com/2624-781X/4/4/37palladium-catalyzed cross-coupling reactiontitaniumterminal alkyneSonogashira-type reactionopen-flask conditions |
| spellingShingle | Yuki Murata Yuya Nishi Mio Matsumura Shuji Yasuike Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes Reactions palladium-catalyzed cross-coupling reaction titanium terminal alkyne Sonogashira-type reaction open-flask conditions |
| title | Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes |
| title_full | Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes |
| title_fullStr | Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes |
| title_full_unstemmed | Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes |
| title_short | Palladium-Catalyzed Cross-Coupling Reaction of Bis(cyclopentadienyl)diaryltitaniums with Terminal Alkynes |
| title_sort | palladium catalyzed cross coupling reaction of bis cyclopentadienyl diaryltitaniums with terminal alkynes |
| topic | palladium-catalyzed cross-coupling reaction titanium terminal alkyne Sonogashira-type reaction open-flask conditions |
| url | https://www.mdpi.com/2624-781X/4/4/37 |
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