Synthesis of Acylsilanes by Copper(I)‐Catalyzed Addition of Silicon Nucleophiles onto Acid Derivatives

Abstract

The transition metal-catalyzed transfer of silicon nucleophiles onto various electrophiles has recently gained considerable attention, due to the now readily available silicon pro-nucleophiles such as silylboronates. Our interest lies in the addition of such species to acid derivatives for the generation of acylsilanes. We report herein an efficient method to synthesize these compounds, starting from easyto-form anhydrides, with very good yields.

Activation of the Si–B interelement bond related to catalysis

“…A mild and practical procedure for the synthesis of acylsilanes by the addition of silylboronic esters to acid derivatives was documented by Riant and co-workers in 2013 (199a-i -200a-i, Scheme 63, top). 85 A screening of different acid derivatives identified symmetrical anhydrides to be the best choice as substrates. A large number of functional groups such as halo (199d and 199e), naphthyl (199f), furyl (199g), and thienyl (199h), were compatible in this reaction, furnishing the In 2019, the Fujihara group disclosed a zinc-mediated addition of silylboronic esters to carboxylic acids (201a-f, i-k -200a-f, i-k, Scheme 64).…”

Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids

“… 14 We reasoned that this strategy could be applied to the intermolecular coupling of an alkene to an appropriately activated carboxylic acid derivative to initially yield an α-chiral ketone, constituting a formal hydroacylation process. 15 , 16 Subsequent reduction of the ketone would additionally yield an alcohol containing two stereocenters. The proposed catalytic cycle ( Scheme 1 c) proceeds via asymmetric Markovnikov hydrocupration of aryl alkene 2 followed by electrophilic interception with an acyl electrophile ( 1 ) to deliver enantioenriched ketone ( 3 ) and L*CuX ( 7 ).…”

Cu-catalyzed enantioselective synthesis of tertiary benzylic copper complexes and their in situ addition to carbonyl compounds

“…Although pioneering studies for catalytic enantioselective allylic alkylation of acyl nucleophiles and ketone enolates to generate tertiary alkyl aryl ketones have been disclosed, 10 – 12 direct catalytic enantioselective nucleophilic addition of an enantioenriched tertiary alkyl–Cu complex to carboxylic acid derivatives remains unprecedented. 13 …”