Acylsilanes are a fascinating class of compounds that display a number of distinctive chemical and physical properties. The unique reactivity pattern of the acylsilane functional group [R-C(O)Si] makes them an increasingly attractive moiety in modern organic synthesis, and as such, they have been utilised in a diverse range of transformations. This review provides an overview of the recent advances in the synthesis and application of acylsilanes in organic chemistry, with a particular focus on the progress made in the last two decades.
The Willgerodt-Kindler reaction has, in recent years, received limited attention and application in synthetic organic chemistry. With the advent of new technology such as microwave-assisted heating, several new, high-yielding, practical, and more environmentally friendly reaction protocols have been developed. This review aims to once again draw attention to this relatively underutilised process by highlighting the recent developments in the Willgerodt-Kindler reaction in the synthesis of (thio)amides, carboxylic acids, and heterocycles.
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A 'Cu'te couple: A synthetically useful protocol for the preparation of N‐alkynylated sulfoximines (yne sulfoximines) has been developed. The method involves a mild copper‐catalyzed oxidative cross‐coupling of NH‐sulfoximines and terminal alkynes (see scheme). The corresponding N‐acyl sulfoximines were also obtained selectively after acid‐catalyzed hydrolysis of the yne sulfoximines.
A high-throughput screen for inhibitors
of the histone acetyltransferase,
KAT6A, led to identification of an aryl sulfonohydrazide derivative
(CTX-0124143) that inhibited KAT6A with an IC50 of 1.0
μM. Elaboration of the structure–activity relationship
and medicinal chemistry optimization led to the discovery of WM-8014
(97), a highly potent inhibitor of KAT6A (IC50 = 0.008 μM). WM-8014 competes with acetyl-CoA (Ac-CoA), and
X-ray crystallographic analysis demonstrated binding to the Ac-CoA
binding site. Through inhibition of KAT6A activity, WM-8014 induces
cellular senescence and represents a unique pharmacological tool.
An oxidative cross-coupling reaction between aldehydes and sulfoximines involving dual C À H/N À H functionalization has been developed. This reaction process is facilitated by a simple copper catalyst (1 mol% loading) and tert-butyl hydroperoxide (TBHP) as the oxidant and proceeds under mild reaction conditions to afford a series of valuable N-acylated sulfoximine derivatives in excellent yields.
A method to access α‐thioaryl ketones and α‐thioaryl esters employing copper acetate (hydrate) as catalyst and readily accessible diaryl disulfides and β‐diketones (or β‐keto esters) has been developed. Both alkyl‐ and aryl‐substituted carbonyl compounds can be prepared.magnified image
A method has been developed for the preparation of N-alkynylated sulfoximines involving the copper-catalyzed decarboxylative coupling of sulfoximines with aryl propiolic acids. A range of substituents on both the sulfoximidoyl moiety and the aryl group of the propiolic acid were compatible with this reaction process to afford a series of sulfoximidoyl-functionalized alkynes.
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