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Remote-Controlled Exchange Rates by Photoswitchable Internal Catalysis of Dynamic Covalent Bonds
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-05-31 , DOI: 10.1021/jacs.2c04658 David N Barsoum 1 , Viraj C Kirinda 1 , Boyeong Kang 1 , Julia A Kalow 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-05-31 , DOI: 10.1021/jacs.2c04658 David N Barsoum 1 , Viraj C Kirinda 1 , Boyeong Kang 1 , Julia A Kalow 1
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The transesterification rate of boronate esters with diols is tunable over 14 orders of magnitude. Rate acceleration is achieved by internal base catalysis, which lowers the barrier for proton transfer. Here we report a photoswitchable internal catalyst that tunes the rate of boronic ester/diol exchange over 4 orders of magnitude. We employed an acylhydrazone molecular photoswitch, which forms a thermally stable but photoreversible intramolecular H-bond, to gate the activity of the internal base catalyst in 8-quinoline boronic ester. The photoswitch is bidirectional and can be cycled repeatedly. The intramolecular H-bond is found to be essential to the design of this photoswitchable internal catalyst, as protonating the quinoline with external sources of acid has little effect on the exchange rate.
中文翻译：
通过动态共价键的光切换内部催化远程控制汇率
硼酸酯与二醇的酯交换速率可调超过 14 个数量级。速率加速是通过内部碱催化实现的，这降低了质子转移的障碍。在这里，我们报告了一种可将硼酸酯/二醇交换速率调整超过 4 个数量级的光可切换内部催化剂。我们使用了一个酰基腙分子光开关，它形成一个热稳定但光可逆的分子内氢键，来控制 8-喹啉硼酸酯中内部碱催化剂的活性。光电开关是双向的，可以反复循环。发现分子内氢键对于设计这种可光切换的内部催化剂至关重要，因为用外部酸源质子化喹啉对交换率几乎没有影响。
更新日期：2022-05-31
中文翻译：
通过动态共价键的光切换内部催化远程控制汇率
硼酸酯与二醇的酯交换速率可调超过 14 个数量级。速率加速是通过内部碱催化实现的，这降低了质子转移的障碍。在这里，我们报告了一种可将硼酸酯/二醇交换速率调整超过 4 个数量级的光可切换内部催化剂。我们使用了一个酰基腙分子光开关，它形成一个热稳定但光可逆的分子内氢键，来控制 8-喹啉硼酸酯中内部碱催化剂的活性。光电开关是双向的，可以反复循环。发现分子内氢键对于设计这种可光切换的内部催化剂至关重要，因为用外部酸源质子化喹啉对交换率几乎没有影响。
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