Is Reaction Acceleration of Microdroplet Chemistry Favorable to Controlling the Enantioselectivity?
Is Reaction Acceleration of Microdroplet Chemistry Favorable to Controlling the Enantioselectivity?
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DOI：
10.1021/acs.joc.3c01660
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发表时间：
2023-11-10
影响因子：
3.6
通讯作者：
Cheng，Heyong
中科院分区：
文献类型：
--
作者：
Zheng，Boyu;Wu，Yikang;Cheng，Heyong
在过去的20年里，微滴化学已经被证明可以惊人地加速许多化学和生物反应。目前微滴加速反应主要是对称合成反应，而非对称合成反应很少涉及立体选择性。本研究选择单分子和双分子反应、多组分Passerini反应和酶促酮还原反应作为模型反应，说明微滴化学的反应加速是否有利于手性中心的保留和对映体选择性的控制。结果表明，微滴化学在反应过程中不会破坏手性起始物已有的立体中心，但在排除酶促反应的情况下，手性催化剂和手性有机配体的不对称催化中会损害立体专一性。我们的初步研究提醒我们在微滴中进行不对称催化时，对产物的对映体选择性要多加注意。希望本研究能对微滴化学立体选择性的进一步研究起到一定的推动作用。
Microdroplet chemistry has been proven to amazingly accelerate many chemical and biological reactions in the past 2 decades. Current microdroplet accelerated reactions are predominantly symmetric synthetic but minorly asymmetric synthetic reactions, where stereoselectivity is scarcely concerned. This study selected unimolecular and bimolecular reactions, multicomponent Passerini reactions, and enzymatic ketone reduction as the model reactions to illustrate whether reaction acceleration of microdroplet chemistry is favorable to retaining a chiral center and controlling the enantioselectivity or not. The results illustrated that microdroplet chemistry did not disrupt pre-existing stereogenic centers in chiral starting materials during reactions but did harm to stereospecificity in asymmetric catalysis by chiral catalysts and chiral organic ligands with the exclusion of enzymatic reactions. Our preliminary study reminds us of more cautions to the product enantioselectivity when conducting asymmetric catalysis in microdroplets. We also hope this study may promote more valuable further research on the stereoselectivity of microdroplet chemistry.