Phosphoric Acid-Catalyzed Asymmetric Synthesis of SPINOL Derivatives

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• 作者：Shaoyu Li ; Ji-Wei Zhang ; Xian-Lin Li ; Dao-Juan Cheng ; Bin Tan
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：December 21, 2016
• 年：2016
• 卷：138
• 期：50
• 页码：16561-16566
• 全文大小：607K
• ISSN：1520-5126

文摘

Axially chiral 1,1′-spirobiindane-7,7′-diol (SPINOL) is the most fundamental and important privileged structure from which other chiral ligands containing a 1,1′-spirobiindane backbone are synthesized. Driven by the development of enantioselective syntheses of axially chiral SPINOL derivatives, we have successfully developed the first phosphoric acid-catalyzed asymmetric approach. This approach is highly convergent and functional group tolerant, efficiently providing SPINOLs in good yield with excellent enantioselectivity, thus delivering a practical and straightforward access to this privileged structure. It should be emphasized that the catalyst loading could be decreased to only 0.1 mol% for the preparative-scale synthesis. Furthermore, 4,4′-dimethyl-SPINOL-phosphoric acid was synthesized and applied to catalyze the model reaction for synthesis of enantioenriched SPINOL derivatives.