Instituto de Catálisis y Petroleoquímica, ICP-CSIC. C/ Marie Curie 2, Madrid 28049, Spain.
Instituto de Nanociencia y Materiales de Aragón (INMA-CSIC), Universidad de Zaragoza, Zaragoza 50009, Spain.
J Am Chem Soc. 2022 May 11;144(18):8249-8256. doi: 10.1021/jacs.2c01874. Epub 2022 May 3.
The development of chiral zeolitic catalysts possessing extra-large pores and endowed with the capability of enantioselectively processing bulky products represents one of the greatest challenges in chemistry. Here, we report the discovery of GTM-3, an enantio-enriched extra-large pore chiral zeolite material with -ITV framework structure, obtained using a simple enantiopure organic cation derived from the chiral pool, ,-ethyl-methyl-pseudoephedrinium, as the chiral-inductor agent. We demonstrate the enantio-enrichment of GTM-3 in one of the two enantiomorphic polymorphs using the two enantiomers of the organic cation. Interestingly, we prove the ability of this zeolitic material to perform enantioselective catalytic operations with very large substrates, here exemplified by the catalytic epoxide aperture of the bulky -stilbene oxide with alcohols, yielding unprecedented product enantiomeric excesses up to 30%. Our discovery opens the way for the use of accessible chiral zeolitic materials for the catalytic asymmetric synthesis of chiral pharmaceutical compounds.
手性沸石催化剂具有超大孔道，能够对大体积产物进行对映选择性处理，其开发是化学领域面临的最大挑战之一。在此，我们报告了 GTM-3 的发现，这是一种具有 -ITV 骨架结构的对映体富集的超大孔手性沸石材料，是使用手性池衍生的简单对映纯有机阳离子，即 -乙基-甲基-假麻黄碱，作为手性诱导剂获得的。我们使用有机阳离子的两种对映异构体证明了 GTM-3 在两种对映异构多晶型体之一中的对映体富集。有趣的是，我们证明了这种沸石材料能够对非常大的底物进行对映选择性催化操作，这里以大体积 -二苯乙烯氧化物与醇的环氧化物开口为例，得到了前所未有的产物对映过量值高达 30%。我们的发现为使用可及的手性沸石材料进行手性药物化合物的催化不对称合成开辟了道路。
