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| 二甲基二茂钛催化芳基端炔合成均三苯及烯炔类衍生物研究 |
| Dimethyltitanocene-Catalyzed Synthesis of Symmetric Triarylbenzenes and Enynyl Derivatives from Terminal Arylalkynes |
| 投稿时间：2025-09-21 修订日期：2025-12-13 |
| DOI： |
| 中文关键词: 二甲基二茂钛 过渡金属卡宾 均三苯衍生物 烯炔类衍生物 |
| 英文关键词:Dimethyltitanocene, Transition Metal Carbene Complex, Symmetric Triarylbenzene Derivatives, Enynyl Derivatives |
| 基金项目:内蒙古自治区自然科学基金项目(2025MS02044) |
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| 中文摘要: |
| 本文以二甲基二茂钛(Cp2TiMe2)为催化剂,采用“一锅法”催化系列芳基端炔化合物合成了1,3,5-三苯基苯 (1a)、1,3,5-三(4-氟苯)基苯 (2a)、1,3,5-三(4-氨基苯)基苯 (3a)、1,3,5-三(4-甲基苯)基苯 (4a)、1,3,5-三(4-甲氧基苯)基苯 (5a)、1,3,5-三二茂铁基苯 (6a)、1,4-二苯基-1-丁烯-3-炔 (1b)、1,4-二(4-氟苯)基-1-丁烯-3-炔 (2b)、1,4-二(4-氨基苯)基-1-丁烯-3-炔 (3b)、1,4-二(4-甲基苯)基-1-丁烯-3-炔 (4b)、1,4-二(4-甲氧基苯)基-1-丁烯-3-炔 (5b)、1,4-二二茂铁基-1-丁烯-3-炔 (6b)、1,4-二(4-苯基苯)基-1-丁烯-3-炔 (7b)等13个均三苯及烯炔类衍生物。底物适应性研究表明,产物收率与芳基空间位阻效应呈负相关性,即空间位阻越小,产物收率越高；反应机理研究显示,Cp2TiMe2受热后形成的二茂钛-亚甲基烯过渡金属卡宾(Cp2Ti=CH2)是催化本反应的关键中间体,其与端炔基团发生加成-重排-裂解反应,通过两条反应路径分别生成均三苯及烯炔类衍生物。本研究较弱的底物适应性在一定程度上限制了该反应的应用前景,但研究本身为茂钛配合物“一锅法”催化合成均三苯、烯炔类衍生物提供了有益的研究思路和技术手段,拓展了茂钛配合物在催化有机合成领域的应用范围。 |
| 英文摘要: |
| This study employs dimethyltitanocene (Cp2TiMe2) as a catalyst to “one-pot” catalyze the synthesis of symmetric triarylbenzene and enynyl derivatives from a series of terminal arylalkynes. The products include 1,3,5-triphenylbenzene (1a), 1,3,5-tris(4-fluorophenyl)-benzene (2a), 1,3,5-tris(4-aminophenyl)-benzene (3a), 1,3,5-tris(4-methylbenzene)-benzene (4a), 1,3,5-tris(4-methoxybenzene)-benzene (5a), 1,3,5-tris(ferrocenyl)benzene (6a), 1,4-diphenyl-1-buten-3-yne (1b), 1,4-bis(4-fluorophenyl)-1-buten-3-yne (2b), 1,4-bis(4-aminophenyl)-1-buten-3-yne (3b), 1,4-bis(4-methylphenyl)-1-buten-3-yne (4b), 1,4-bis(4-methoxyphenyl)-1-buten-3-yne (5b), 1,4-diferrocenyl-1-buten-3-yne (6b), 1,4-bis(4-phenylphenyl)-1-buten-3-yne (7b). Substrate scope investigation revealed an inverse correlation between product yield and the steric hindrance of the aryl substituents, indicating that smaller steric hindrance leads to higher yields. Mechanistic studies demonstrated that titanocene-methylidene (Cp2Ti=CH2), a transition metal carbene intermediate formed upon thermal activation of Cp2TiMe2, is the key species catalyzing this reaction. It undergoes addition-rearrangement-cleavage sequences with terminal arylalkynes, leading to the formation of symmetric triarylbenzenes and enynyl derivatives via two distinct reaction pathways. The limited substrate scope of this study has somewhat restricted the application prospects of the reaction. However, the study itself provides valuable research ideas and technical approaches for the “one-pot” catalytic synthesis of mesitylene and enyne derivatives using titanocene complexes, thereby expanding the application range of titanocene complexes in the field of catalytic organic synthesis. |
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