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Screening of a phosphite-phosphoramidite ligand library for palladium-catalysed asymmetric allylic substitution reactions: The origin of enantioselectivity

机译:钯催化的不对称烯丙基取代反应的亚磷酸酯-亚磷酰胺配体库的筛选:对映选择性的起源

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摘要

We have designed a new library of readily available, highly modular phosphite-phosphoramidite ligands for asymmetric allylic substitution reactions. They are easily prepared in one step from commercially available chiral 1,2-amino alcohols. The introduction of a phosphoramidite moiety into the ligand design is highly advantageous for the product outcome. This ligand library affords high reaction rates (TOFs of up to 800 mol (mol h)(-1)) and enantioselectivities (ees of up to 99%) and, at the same time, contains a broad range of disubstituted hindered and unhindered substrate types. NMR study of the Pd-pi-allyl intermediates provide a deeper understanding of the effect of the ligand parameters on the origin of enantioselectivity.
机译:我们设计了一个新的易于使用的,高度模块化的亚磷酸酯-亚磷酰胺配体库,用于不对称的烯丙基取代反应。它们可以很容易地从市售的手性1,2-氨基醇中一步制备。将亚磷酰胺部分引入配体设计中对于产物结果是高度有利的。该配体库可提供高反应速率(TOF高达800 mol(mol h)(-1))和对映体选择性(ee高达99%),同时包含多种双取代的受阻和不受阻底物类型。 Pd-pi-烯丙基中间体的NMR研究提供了对配体参数对对映选择性起源的影响的更深刻的理解。

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