C3−H Silylation of Furfurylimines: Direct Access to a Novel Biobased Versatile Synthetic Platform Derived from Furfural. Issue 7 (14th June 2022)

• Record Type: Journal Article
• Authors: Curpanen, Sebastien; Poli, Giovanni; Perez‐Luna, Alejandro; Oble, Julie
• Is Part Of: Asian journal of organic chemistry. Volume 11:Issue 7(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-06-14
• Subjects: Biomass -- Fluoride -- Furfural -- Iridium -- Silicon; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.202200199
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: Herein we report directed iridium‐catalyzed C3−H silylation of furfuryl imines, which grants access to versatile synthetic platforms. This transformation was developed on furfuryl derivatives, using imines as directing groups, and trialkylsilanes or bis(trimethylsilyl)methylsilane as silylating agents, in the presence of a hydride scavenger. Subsequently, fluoride‐mediated activation strategies were applied to the C3−SiMe(OSiMe3 )2 furfural derivatives to achieve a wide range of transformations of the C3−Si bond. Arylation, alkenylation, alkynylation, allylation and alkylation, as well as halogenation and trifluoromethylation were achieved in modest to high yields. A variety of high value‐added products were thus easily obtained from the same common C3‐silylated furfural‐based platform. Abstract : Promising C3‐silylated furfural platform : Iridium‐catalyzed selective C3−H silylation of biomass‐derived furfural derivatives with hydrosilanes provides access to versatile C3‐silylated platforms. Furthermore, C3−SiMe(OTMS)2 furfurals offer direct access to a set of novel value‐added furfurals through fluoride‐mediated functionalizations of the C(sp 2 )−Si bond, namely arylation, alkenylation, alkynylation, allylation and alkylation, as well as halogenation and trifluoromethylation.