En Route to the Transformation of Glycoscience: A Chemist’s Perspective on Internal and External Crossroads in Glycochemistry,Journal of the American Chemical Society

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En Route to the Transformation of Glycoscience: A Chemist’s Perspective on Internal and External Crossroads in Glycochemistry
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-12-22 , DOI: 10.1021/jacs.0c11106
David Crich _{1,

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Affiliation

Carbohydrate chemistry is an essential component of the glycosciences and is fundamental to their progress. This Perspective takes the position that carbohydrate chemistry, or glycochemistry, has reached three crossroads on the path to the transformation of the glycosciences, and illustrates them with examples from the author's and other laboratories. The first of these potential inflexion points concerns the mechanism of the glycosylation reaction and the role of protecting groups. It is argued that the experimental evidence supports bimolecular SN2-like mechanisms for typical glycosylation reactions over unimolecular ones involving stereoselective attack on naked glycosyl oxocarbenium ions. Similarly, it is argued that the experimental evidence does not support long-range stereodirecting participation of remote esters through bridged bicyclic dioxacarbenium ions in organic solution in the presence of typical counterions. Rational design and improvement of glycosylation reactions must take into account the roles of the counterion and of concentration. A second crossroads is that between mainstream organic chemistry and glycan synthesis. The case is made that the only real difference between glycan and organic synthesis is the formation of C-O rather than C-C bonds, with diastereocontrol, strategy, tactics, and elegance being of critical importance in both areas: mainstream organic chemists should feel comfortable taking this fork in the road, just as carbohydrate chemists should traveling in the opposite direction. A third crossroads is that between carbohydrate chemistry and medicinal chemistry, where there are equally many opportunities for traffic in either direction. The glycosciences have advanced enormously in the past decade or so, but creativity, input, and ingenuity of scientists from all fields is needed to address the many sophisticated challenges that remain, not the least of which is the development of a broader and more general array of stereospecific glycosylation reactions.

中文翻译：

糖科学的变革之路：化学家对糖化学内部和外部十字路口的看法

碳水化合物化学是糖科学的重要组成部分，也是糖科学进步的基础。本观点认为碳水化合物化学或糖化学在糖科学转型的道路上已经到达了三个十字路口，并用作者和其他实验室的例子来说明它们。这些潜在拐点中的第一个涉及糖基化反应的机制和保护基团的作用。有人认为，实验证据支持典型糖基化反应的双分子 SN2 样机制，而不是单分子糖基化反应，涉及对裸露糖基氧碳鎓离子的立体选择性攻击。同样，有人认为，实验证据不支持在典型抗衡离子存在的有机溶液中通过桥联双环二氧碳鎓离子远程酯参与远程立体定向。糖基化反应的合理设计和改进必须考虑反离子和浓度的作用。第二个十字路口是主流有机化学和聚糖合成之间的十字路口。事实证明，聚糖和有机合成之间唯一真正的区别是 CO 键而不是 CC 键的形成，非对映控制、策略、策略和优雅在这两个领域都至关重要：主流有机化学家应该放心地接受这个分支在路上，就像碳水化合物化学家应该朝相反的方向行驶一样。第三个十字路口是碳水化合物化学和药物化学之间的十字路口，两个方向都有同样多的交通机会。糖科学在过去十年左右的时间里取得了巨大的进步，但需要来自各个领域的科学家的创造力、投入和独创性来解决仍然存在的许多复杂的挑战，其中最重要的是开发更广泛和更通用的系列立体特异性糖基化反应。

更新日期：2020-12-22

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