Novel Bis(1,3,2-diazaphospholidine) Ligands for Asymmetric Catalysis

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• 作者：Inmaculada Arribas ; Eleuterio 脕lvarez ; Antonio Pizzano
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 13, 2013
• 年：2013
• 卷：32
• 期：9
• 页码：2497-2500
• 全文大小：237K
• 年卷期：v.32,no.9(May 13, 2013)
• ISSN：1520-6041

文摘

A family of modularly designed chiral bis(1,3,2-diazaphospholidines) with N-aryl substituents (NP-PN) is reported. These compounds have been prepared in two steps from readily available (R,R)-1,2-diaminocyclohexane and tetrachlorodiphosphines. Examples in the set differ in the backbone and the aryl substituents, aiming at their application in asymmetric catalysis. Thus, [Rh(NBD)(NP-PN)]BF₄ complexes lead to active catalysts in the hydrogenation of methyl 伪-acetamidoacrylate, which provide enantioselectivities up to 96% ee. In addition, NP-PN ligands also generate active catalysts in the hydroformylation of vinyl acetate, leading to high regioselectivities (iso:n ratio higher than 99:1) and enantioselectivities up to 65% ee.