Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON N9B 3P4, Canada.
Molecules. 2022 May 11;27(10):3078. doi: 10.3390/molecules27103078.
The generation of ε-carbonyl cations and their reactions with nucleophiles is accomplished readily without transition metal cation stabilization, using the ε-bromide dienoate or dienone starting materials and GaCl or InCl catalysis. Arene nucleophiles are somewhat more straightforward than allyltrimethylsilane, but allyltrimethylsilane and propiophenone trimethysilyl enol ether each react successfully with InCl catalysis. The viability of these cations is supported by DFT calculations.
利用 ε-溴代二烯酸酯或二烯酮起始原料和 GaCl 或 InCl 催化,无需过渡金属阳离子稳定化,即可轻松实现 ε-羰基阳离子的生成及其与亲核试剂的反应。芳基亲核试剂比烯丙基三甲基硅烷更为直接,但烯丙基三甲基硅烷和丙酰苯甲酮三甲硅基烯醇醚在 InCl 催化下均能成功反应。这些阳离子的可行性得到了 DFT 计算的支持。