C−H Activation of Alkanes, Alkenes, Alkynes, Arenes, and Ethers Using a Stannylene/Aryl Halide Mixture†
C−H Activation of Alkanes, Alkenes, Alkynes, Arenes, and Ethers Using a Stannylene/Aryl Halide Mixture†
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DOI：
10.1021/om100267a
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发表时间：
2010-10
期刊：
影响因子：
2.8
通讯作者：
Ajdin Kavara;Thaddeus T. Boron;Zubair S. Ahsan;M. Holl
中科院分区：
文献类型：
--
作者：
Ajdin Kavara;Thaddeus T. Boron;Zubair S. Ahsan;M. Holl
SnC(SiMe3)2CH2CH2C(SiMe3)2/ArI (Ar = Ph, 2,4,6-三异丙基苯基)与环己烷、乙醚、四氢呋喃 (THF)、甲苯和均三甲苯的反应产生 CH 活化产物，其中在最弱的 CH 键位置形成新的 Sn−C 键。探索了反式 4-甲基-2-戊烯和 4-甲基-2-戊炔反应的区域选择性与芳基卤化物对 PhI、2,4,6-三甲基碘苯、2,4,6-三异丙基碘苯、4-碘茴香醚、4-碘苯甲腈和 2,6-异亚甲基碘苯的反应。正如初级激活量增加所强调的那样，可以获得一定程度的区域化学控制。在所有尝试的溶剂中，2,4,6-叔丁基碘苯的使用都会导致邻叔丁基的 C−H 活化。 SnC(SiMe3)2CH2CH2C(SiMe3)2/2,4,6-三异丙基碘苯与甲苯/甲苯-d7 反应的主要动力学同位素效应为 4.9 ± 0.5。
The reaction of SnC(SiMe3)2CH2CH2C(SiMe3)2/ArI (Ar = Ph, 2,4,6-triisopropylphenyl) with cyclohexane, diethyl ether, tetrahydrofuran (THF), toluene, and mesitylene yields C−H activation products in which a new Sn−C bond is formed at the location of the weakest C−H bond. The regioselectivity of this reaction with trans-4-methyl-2-pentene and 4-methyl-2-pentyne was explored as a function of aryl halide for PhI, 2,4,6-trimethyliodobenzene, 2,4,6-triisopropyliodobenzene, 4-iodoanisole, 4-iodobenzonitrile, and 2,6-mesityliodobenzene. A degree of regiochemical control could be obtained as highlighted by increased amounts of primary activation. The use of 2,4,6-tert-butyliodobenzene resulted in C−H activation of the ortho tert-butyl groups in all solvents tried. The primary kinetic isotope effect for the reaction of SnC(SiMe3)2CH2CH2C(SiMe3)2/2,4,6-triisopropyliodobenzene with toluene/toluene-d7 was found to be 4.9 ± 0.5.