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Mechanisms of Stereodirecting Participation and Ester Migration from Near and Far in Glycosylation and Related Reactions.
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-07-05 , DOI: 10.1021/acs.chemrev.0c00243 Asiri A Hettikankanamalage 1, 2 , Robert Lassfolk 3 , Filip S Ekholm 4 , Reko Leino 3 , David Crich 1, 2, 5
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-07-05 , DOI: 10.1021/acs.chemrev.0c00243 Asiri A Hettikankanamalage 1, 2 , Robert Lassfolk 3 , Filip S Ekholm 4 , Reko Leino 3 , David Crich 1, 2, 5
Affiliation
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This review is the counterpart of a 2018 Chemical Reviews article (Adero, P. O.; Amarasekara, H.; Wen, P.; Bohé, L.; Crich, D. Chem. Rev.2018, 118, 8242–8284) that examined the mechanisms of chemical glycosylation in the absence of stereodirecting participation. Attention is now turned to a critical review of the evidence in support of stereodirecting participation in glycosylation reactions by esters from either the vicinal or more remote positions. As participation by esters is often accompanied by ester migration, the mechanism(s) of migration are also reviewed. Esters are central to the entire review, which accordingly opens with an overview of their structure and their influence on the conformations of six-membered rings. Next the structure and relative energetics of dioxacarbeniun ions are covered with emphasis on the influence of ring size. The existing kinetic evidence for participation is then presented followed by an overview of the various intermediates either isolated or characterized spectroscopically. The evidence supporting participation from remote or distal positions is critically examined, and alternative hypotheses for the stereodirecting effect of such esters are presented. The mechanisms of ester migration are first examined from the perspective of glycosylation reactions and then more broadly in the context of partially acylated polyols.
中文翻译：
糖基化及相关反应中的立体定向参与和酯从近处和远处迁移的机制。
该综述与 2018 年《化学评论》文章（Adero, PO; Amarasekara, H.; Wen, P.; Bohé, L.; Crich, D. Chem. Rev. 2018 , 118 , 8242–8284）相对应，该文章审查了在没有立体定向参与的情况下化学糖基化的机制。现在的注意力转向对支持来自邻近或更远位置的酯立体定向参与糖基化反应的证据进行严格审查。由于酯的参与通常伴随着酯迁移，因此还回顾了迁移的机制。酯是整个综述的核心，因此首先概述了它们的结构及其对六元环构象的影响。接下来介绍二氧碳烯离子的结构和相对能量学，重点是环尺寸的影响。然后介绍现有的参与动力学证据，然后概述各种分离或光谱表征的中间体。对支持远程或远端位置参与的证据进行了严格的审查，并提出了此类酯的立体定向效应的替代假设。首先从糖基化反应的角度研究酯迁移的机制，然后在部分酰化多元醇的背景下更广泛地研究酯迁移的机制。
更新日期：2020-08-12
中文翻译：
糖基化及相关反应中的立体定向参与和酯从近处和远处迁移的机制。
该综述与 2018 年《化学评论》文章（Adero, PO; Amarasekara, H.; Wen, P.; Bohé, L.; Crich, D. Chem. Rev. 2018 , 118 , 8242–8284）相对应，该文章审查了在没有立体定向参与的情况下化学糖基化的机制。现在的注意力转向对支持来自邻近或更远位置的酯立体定向参与糖基化反应的证据进行严格审查。由于酯的参与通常伴随着酯迁移，因此还回顾了迁移的机制。酯是整个综述的核心，因此首先概述了它们的结构及其对六元环构象的影响。接下来介绍二氧碳烯离子的结构和相对能量学，重点是环尺寸的影响。然后介绍现有的参与动力学证据，然后概述各种分离或光谱表征的中间体。对支持远程或远端位置参与的证据进行了严格的审查，并提出了此类酯的立体定向效应的替代假设。首先从糖基化反应的角度研究酯迁移的机制，然后在部分酰化多元醇的背景下更广泛地研究酯迁移的机制。
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