Ligand and base additive effects on the reversibility of nucleophilic addition in palladium-catalyzed allylic aminations monitored by nucleophile crossover

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• 作者：Bryan S. Holtzman^a ; Eric T. Roberts^a ; Nicholas S. Caminiti^a ; Jacob A. Fox^a ; Madison B. Goodstein^a ; Staci A. Hill^a ; Zitong B. Jia^a ; Isabelle N.-M. Leibler^a ; Michael L. Martini^a ; Gina M. Mendolia^a ; Sarah B. Nodder^a ; Molly S. Costanza-Robinson^b ; Richard C. Bunt^a ; ^{rbunt@middlebury.edu}
• 关键词：Palladium catalysis ; Allylic amination ; Reversibility ; Ligand effects ; Elimination
• 刊名：Tetrahedron Letters
• 出版年：2017
• 出版时间：1 February 2017
• 年：2017
• 卷：58
• 期：5
• 页码：432-436
• 全文大小：789 K
• 卷排序：58

文摘

Nucleophile crossover quantitates reversibility of benzylamine addition. DBU and Cs2CO3 inhibit crossover/reversibility with all ligands tested. Cs2CO3 causes much less elimination to dienes than DBU. Percent conversion analysis shows timing of crossover/reversibility. Results support reversibility as mechanism for base effects on enantioselectivity.