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Friedel−Crafts‐Type Allylation of Phenol Derivatives Catalyzed by In Situ‐Generated Silyl Cyanometallates

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Title: Friedel−Crafts‐Type Allylation of Phenol Derivatives Catalyzed by In Situ‐Generated Silyl Cyanometallates
Authors: Yurino, Taiga Browse this author →KAKEN DB
Ece, Hamdiye Browse this author
Ohkuma, Takeshi Browse this author →KAKEN DB
Keywords: Silyl Lewis acid
Friedel-Crafts reaction
Allylic substitution
Ag catalyst
Pd catalyst
Issue Date: Apr-2020
Publisher: Wiley
Journal Title: Asian Journal of Organic Chemistry
Volume: 9
Issue: 4
Start Page: 557
End Page: 560
Publisher DOI: 10.1002/ajoc.202000023
Abstract: We successfully demonstrated that Friedel−Crafts‐type allylation of phenol derivatives and allylic phosphates is catalyzed by the AgTFA/trimethylsilyl cyanide (Me3SiCN) and Pd(OAc)2/Me3SiCN combined systems to afford the C‐allylated product in a highly regioselective manner. The corresponding silyl cyanometallates generated in situ are proposed to be the active catalytic species. Lewis acidity of the reversibly formed ion pairs is appropriately regulated for this reaction. The para‐allylated anisole and phenol derivatives are selectively obtained. The para‐substituted ones are converted to the ortho‐allylated products. The reactivity of the catalytic systems is strongly dependent on the electronic nature of both electrophile and nucleophile. Substitution of an aromatic ring on the allylic phosphate is essential for the reaction. Thus, the competitive reaction of a 1 : 1 mixture of cinnamyl and simple allyl phosphates affords only the cinnamyl‐substituted product.
Rights: This is the peer-reviewed version of the following article: T. Yurino, H. Ece, T. Ohkuma, Asian J. Org. Chem. 2020, 9, 557. , which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-Archiving.
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 大熊 毅

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