The generally accepted hypothesis to explain the origin of biological homochirality (that is to say, the fact that proteinogenic amino acids are left-handed, and carbohydrates right-handed, in all living beings) is to assume, in the course of prebiotic chemical evolution, the appearance of an initial enantiomeric excess in a set of chiral molecular entities by spontaneous mirror-symmetry breaking (SMSB), together with suitable amplification and replication mechanisms that overcome the thermodynamic drive to racemization. However, the achievement of SMSB in chemical reactions taking place in solution requires highly specific reaction networks showing nonlinear dynamics based on enantioselective autocatalysis, and examples of its experimental realization are very rare. On the other hand, emergence of net supramolecular chirality by SMSB in the self-assembly of achiral molecules has been seen to occur in several instances, and the chirality sign of the resulting supramolecular system can be controlled by the action of macroscopic chiral forces. These considerations led us to propose a new mechanism for the generation of net chirality in molecular systems, in which the SMSB takes place in the formation of chiral supramolecular dissipative structures from achiral monomers, leading to asymmetric imbalances in their composition that are subsequently transferred to a standard enantioselective catalytic reaction, dodging in this way the highly limiting requirement of finding suitable reactions in solution that show enantio­selective autocatalysis. We propose the name ‘absolute asymmetric catalysis’ for this approach, in which an achiral monomer is converted into a nonracemic chiral aggregate that is generated with SMSB and that is catalytically active.Our aim in this Account is to present a step-by-step narrative of the conceptual and experimental development of this hitherto unregarded, but prebiotically plausible, mechanism for the emergence of net chirality in molecular reactions.1 Introduction: The Origin of Biological Homochirality and Spontaneous Mirror-Symmetry Breaking2 Experimental Chemical Models for Spontaneous Mirror-Symmetry Breaking: The Soai Reaction and Beyond3 Spontaneous Mirror-Symmetry Breaking in Supramolecular Chemistry: Plenty of Room at the Top4 Absolute Asymmetric Catalysis: An Alternative Mechanism for the Emergence of Net Chirality in Molecular Systems 5 Experimental Realization of Top-Down Chirality Transfer to the Molecular Level6 Conclusions and Outlook

中文翻译：

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绝对不对称催化，从概念到实验：叙述

解释生物同手性起源的普遍接受的假设（也就是说，在所有生物中，蛋白质氨基酸是左旋的，碳水化合物是右旋的这一事实）是假设，在生命前的化学进化过程中，通过自发镜像对称破坏（SMSB）在一组手性分子实体中出现初始对映体过量，以及克服热力学驱动外消旋化的合适的放大和复制机制。然而，在溶液中发生的化学反应中实现 SMSB 需要高度特异性的反应网络，显示基于对映选择性自催化的非线性动力学，其实验实现的例子非常罕见。另一方面，在非手性分子的自组装过程中，SMSB 出现净超分子手性的现象已经出现在几种情况下，并且由此产生的超分子系统的手性符号可以通过宏观手性力的作用来控制。这些考虑使我们提出了一种在分子系统中产生净手性的新机制，其中 SMSB 发生在从非手性单体形成手性超分子耗散结构的过程中，导致其组成的不对称不平衡，随后转移到标准的对映选择性催化反应，以这种方式避免了在溶液中寻找合适的反应以显示对映选择性自动催化的高度限制要求。我们建议将这种方法命名为“绝对不对称催化”，