端炔偶联反应中铜变价催化机制的理论研究
收稿日期: 2021-12-30
修回日期: 2022-01-25
网络出版日期: 2022-02-18
基金资助
国家自然科学基金(11704024); 国家自然科学基金(21973024); 河北省自然科学基金(B2020201006); 河北大学人才引进项目(521000981133); 河北大学在读研究生创新能力培养(HBU2021ss021); 河北大学2021年课程思政教学改革研究(KCSZ21053); 河北大学第三批“精品实验项目”(2021-BZ-JPSY37); 河北大学大学生创新创业训练计划项目(2020281); 河北大学大学生创新创业训练计划项目(2021184); 河北大学化学与环境科学学院第二批本科教学改革(H2-04004); 河北大学化学与环境科学学院第二批本科教学改革(H2-06001)
Theoretical Study on the Catalytic Mechanism of Copper with Various Valence for the Terminal Alkyne Coupling Reaction
Received date: 2021-12-30
Revised date: 2022-01-25
Online published: 2022-02-18
Supported by
National Natural Science Foundation of China(11704024); National Natural Science Foundation of China(21973024); Natural Science Foundation of Hebei Province(B2020201006); Advanced Talents Incubation Program of the Hebei University(521000981133); Post-Graduate's Innovation Fund Project of Hebei University(HBU2021ss021); 2021 Curriculum Ideological and Political Education of Hebei University(KCSZ21053); Third Excellent Experimental Project of Hebei University(2021-BZ-JPSY37); College Studentsʼ Innovation and Entrepreneurship Training Program of Hebei University(2020281); College Studentsʼ Innovation and Entrepreneurship Training Program of Hebei University(2021184); Teaching and Reform Project of College of Chemistry & Environmental Science, Hebei University(H2-04004); Teaching and Reform Project of College of Chemistry & Environmental Science, Hebei University(H2-06001)
铜催化端炔对称偶联是合成共轭二炔的重要反应. 基于密度泛函理论和Marcus公式, 研究了苯乙炔(Phenylacetylene, PAY)对称偶联的铜变价催化机制. 结果表明, 在有机溶剂中PAY优先与一价铜络合物配位, 并经单电子转移变为二价铜络合的端炔1. 端炔1经质子消除生成一价铜炔化物2. 2与PAY加成为铜炔化物3. 3经分子内H转移、Csp—Csp偶联、配体交换生成1,4-二苯基丁二炔(1,4-Diphenyl-1,3-butadiyne, DPBY); 或3经分子间质子消除、 Csp—Csp偶联、单电子转移以及配体交换反应生成DPBY. 此外, 强碱条件下易生成PAY–, PAY–与2加成为铜炔化物3', 3'经歧化反应(单重态和三重态势能面交叉)生成铜炔化物14, 14解离得到DPBY. 电荷分析表明, 上述反应过程存在一价和零价中间体以及过渡态, 解释了文献中测得多种不同价态铜络合物的原因.
马丽文 , 魏晓叶 , 赵紫琳 , 赵昂 , 邓祥文 , 霍丙南 , 马刚 , 张春芳 . 端炔偶联反应中铜变价催化机制的理论研究[J]. 有机化学, 2022 , 42(6) : 1811 -1819 . DOI: 10.6023/cjoc202112041
Copper-catalyzed homo-coupling reaction of terminal alkynes is of significant importance for the synthesis of conjugated diynes. Based on density functional theory and Marcus formula, the reaction mechanism for the copper-catalyzed homo-coupling reaction of phenylacetylene (PAY) is reported. Our calculations show that PAY is preferentially coordinated with the cuprous complexes in different organic solvents, which is transferred to Cu(II)-acetylide (complex 1) by single electron transfer reaction. Complex 1 is subsequently transferred to Cu(I)-acetylide (complex 2) by proton elimination reaction. Another PAY is added to complex 2 forming complex 3, of which the terminal H is transferred intramolecularly. Followed by Csp—Csp coupling and ligand exchange reactions, 1,4-diphenyl-1,3-butadiyne (DPBY) is obtained. Besides, the complex 3 could also become DPBY via subsequent intermolecular proton elimination, Csp—Csp coupling, SET and ligand exchange reactions. In addition, under the strong base condition, phenylacetylene anion (PAY–) is generated and then add to complex 2 forming complex 3'. Complex 3' then changes into complex 14 through disproportionation reaction, where the singlet-triplet coupling is involved. Complex 14 is dissociated into DPBY directly. The charges are computed for all the involved complexes, which are Cu(0)/(I) intermediates and Cu(II)/(I) transition states, illustrating the observed copper species with different valence in experiments.
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