Catalytic Enantioselective Synthesis of C₁- and C₂-Symmetric Spirobiindanones through Counterion-Directed Enolate C-Acylation

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• 作者：Benjamin F. Rahemtulla ; Hugh F. Clark and Prof. Dr. Martin D. Smith
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：October 10, 2016
• 年：2016
• 卷：55
• 期：42
• 页码：13180-13183
• 全文大小：1424K
• ISSN：1521-3773

文摘

A catalytic enantioselective route to C₁- and C₂-symmetric 2,2′-spirobiindanones has been realized through an intramolecular enolate C-acylation. This reaction employs a chiral ammonium counterion to direct the acylation of an in situ generated ketone enolate with a pentafluorophenyl ester. This reaction constitutes the first example of a direct catalytic enantioselective C-acylation of a ketone and provides an efficient and highly enantioselective route to axially chiral spirobiindanediones. These products can be diastereoselectively derivatized, offering access to a range of functionalized spirocyclic architectures.