Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules.
Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules.
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CIS-1,2-二醇的催化剂识别可以使复杂分子的位点选择性功能化。
作者：
碳水化合物和天然产物在自然界中发挥着重要作用，也为药物和疫苗提供了核心支架。然而，这些分子的固有复杂性对其选择性官能化和衍生化施加了显著的合成障碍。自然界已经通过采用能够在手性口袋内定向和激活底物的酶来部分解决这些问题，这大大提高了有机转化的速率和选择性。在这篇文章中，我们表明，类似的邻近效应可以利用在合成催化剂的背景下，实现一般和可预测的复杂分子的位点选择性功能化。与酶不同，我们的催化剂应用单个可逆共价键来识别并结合底物内的特定官能团。通过将这种独特的结合选择性和不对称催化相结合，我们能够修饰单糖和天然产物中反应性较低的轴向位置。
Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has in part addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which dramatically increases both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products.
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影响因子：
56.9
作者：
Chen, Mark S.;White, M. Christina
通讯作者：
White, M. Christina
固有的和引导的 C-H 功能化逻辑。
影响因子：
18.3
作者：
Brueckl, Tobias;Baxter, Ryan D.;Ishihara, Yoshihiro;Baran, Phil S.
通讯作者：
Baran, Phil S.
影响因子：
5.2
作者：
Beale, Thomas M.;Taylor, Mark S.
通讯作者：
Taylor, Mark S.
影响因子：
2.1
作者：
Griswold, KS;Miller, SJ
通讯作者：
Miller, SJ
影响因子：
15
作者：
Kawabata, Takeo;Muramatsu, Wataru;Schedel, Hartmut
通讯作者：
Schedel, Hartmut