Relevance of the Entropy Factor in Stereoselectivity Control of Asymmetric Photoreactions
Relevance of the Entropy Factor in Stereoselectivity Control of Asymmetric Photoreactions
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熵因子在不对称光反应立体选择性控制中的相关性
DOI：
10.1055/s-0040-1707962
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发表时间：
2021
期刊：
影响因子：
2
通讯作者：
Mori Tadashi
中科院分区：
文献类型：
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作者：
Nagata Yuya;Mori Tadashi;武智 紳吾・津留崎 陽大・神川 憲;田原 紗奈・津留崎 陽大・神川 憲;Mori Tadashi
熵和焓因子在平衡和反应等各种化学现象中起着重要的作用。然而，熵因子在大多数情况下经常被低估，特别是在合成化学中。实际上，熵因子可以与焓因子竞争，或者甚至可以在确定分子相互作用和化学转化时的总自由能或活化能变化中起决定性作用，特别是在基态和/或激发态中的弱相互作用是显著的情况下。在这个帐户中，我们概述了熵因子在各种化学现象中的热力学和动力学，在基态和激发态的重要性。很明显，许多非对映体和对映体选择性光反应是熵控制的。进一步讨论了不对称光反应中熵控制概念的最新进展。理解熵控制概念将为改进、微调甚至逆转相关化学现象的化学和立体选择性铺平道路。1引言2熵在超分子相互作用中的作用3熵驱动的热反应的选定实例4光反应中熵控制的经典实例5熵驱动的不对称光反应6熵控制的进展7前景
Entropy as well as enthalpy factors play substantial roles in various chemical phenomena such as equilibrium and reactions. However, the entropy factors are frequently underestimated in most instances, particularly in synthetic chemistry. In reality, the entropy factor can be in competition with the enthalpy factor or can even be decisive in determining the overall free or activation energy change upon molecular interaction and chemical transformation, particularly where weak interactions in ground and/or excited states are significant. In this account, we overview the importance of the entropy factor in various chemical phenomena in both thermodynamics and kinetics and in the ground and excited states. It is immediately apparent that many diastereo- and enantioselective photoreactions are entropy-controlled. Recent advances on the entropy-control concept in asymmetric photoreactions are further discussed. Understanding the entropy-control concept will pave the way to improve, fine-tune, and even invert the chemo- and stereoselectivity of relevant chemical phenomena.1 Introduction2 Role of Entropy in Supramolecular Interactions3 Selected Examples of Entropy-Driven Thermal Reactions4 Classical Examples of Entropy Control in Photoreactions5 Entropy-Driven Asymmetric Photoreactions6 Advances in Entropy Control7 Perspective