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Nanoscale and chiral metal–organic frameworks for asymmetric reactions in water: bridging Lewis acid catalysis and biological systems
Chemical Science ( IF 7.6 ) Pub Date : 2024-05-06 , DOI: 10.1039/d4sc01343c Watchara Srimontree 1 , Taku Kitanosono 1 , Yasuhiro Yamashita 1 , Shū Kobayashi 1
Chemical Science ( IF 7.6 ) Pub Date : 2024-05-06 , DOI: 10.1039/d4sc01343c Watchara Srimontree 1 , Taku Kitanosono 1 , Yasuhiro Yamashita 1 , Shū Kobayashi 1
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Nowadays, stereoselective control over the sheer variety of chemical transformations benefits from the multipotency of chiral Lewis acids. Their use under biocompatible conditions has long posed a challenge because profuse amounts of biogenic nucleophiles readily deactivate them. To bridge the gap between chiral Lewis acid catalysis and biocompatible chemistry, the conversion of UiO(BPY)-type nanosized metal–organic frameworks (NMOFs) into chiral variants was herein exemplified. The combination of an elongated 2,2′-bipyridyl linker and scandium salt with a hydrophobic anion proved essential to implement traits such as robustness, biocompatibility, and catalytic activity. The catalyst could construct sufficiently hydrophobic environments sequestered within the framework, catalyzing asymmetric ring-opening reactions of meso-epoxide with low catalyst loading to afford β-amino acid alcohols in high yield (up to >99%) with high enantioselectivity (up to 88%). Most impressively, it exhibited a tolerance to the ex vivo poisoning of chiral Lewis acid catalysis by biogenic nucleophiles in sharp contrast to conventional water-compatible Lewis acids.
中文翻译：
用于水中不对称反应的纳米级和手性金属有机框架：桥接路易斯酸催化和生物系统
如今，对各种化学转化的立体选择性控制受益于手性路易斯酸的多效性。它们在生物相容性条件下的使用长期以来一直构成挑战，因为大量的生物亲核试剂很容易使它们失活。为了弥合手性路易斯酸催化和生物相容性化学之间的差距，本文举例说明了将 UiO(BPY) 型纳米金属有机框架 (NMOF) 转化为手性变体。延长的 2,2'-联吡啶连接体和钪盐与疏水性阴离子的组合被证明对于实现鲁棒性、生物相容性和催化活性等特性至关重要。该催化剂可以在框架内构建足够的疏水性环境，以低催化剂负载量催化内消旋环氧化物的不对称开环反应，以高收率（高达> 99％）和高对映选择性（高达88）提供β-氨基酸醇。 %）。最令人印象深刻的是，它表现出对生物亲核试剂对手性路易斯酸催化的离体中毒的耐受性，这与传统的水相容性路易斯酸形成鲜明对比。
更新日期：2024-05-06
中文翻译：
用于水中不对称反应的纳米级和手性金属有机框架：桥接路易斯酸催化和生物系统
如今，对各种化学转化的立体选择性控制受益于手性路易斯酸的多效性。它们在生物相容性条件下的使用长期以来一直构成挑战，因为大量的生物亲核试剂很容易使它们失活。为了弥合手性路易斯酸催化和生物相容性化学之间的差距，本文举例说明了将 UiO(BPY) 型纳米金属有机框架 (NMOF) 转化为手性变体。延长的 2,2'-联吡啶连接体和钪盐与疏水性阴离子的组合被证明对于实现鲁棒性、生物相容性和催化活性等特性至关重要。该催化剂可以在框架内构建足够的疏水性环境，以低催化剂负载量催化内消旋环氧化物的不对称开环反应，以高收率（高达> 99％）和高对映选择性（高达88）提供β-氨基酸醇。 %）。最令人印象深刻的是，它表现出对生物亲核试剂对手性路易斯酸催化的离体中毒的耐受性，这与传统的水相容性路易斯酸形成鲜明对比。
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