Photoinduced acyl transfer

Abstract

The acylation reaction occupies a central role in biochemistry and organic synthesis. On the one hand, it is by this very reaction that amino acids successively assemble to form peptides and proteins, and on the other hand it is a major synthetic method encompassing esterification, amidation, Friedel-Crafts reaction and many other processes routinely used both at the laboratory and the industrial scale. Photochemical activation is always an attractive alternative, because it is relatively mild (provided innocuous wavelengths are used), and no additional substance is added; thus no separation of the activator is necessary at the end of the process. In this paper, we briefly survey the most widely used methods of photoinduced acylations, and our own contribution to the field.

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

“…More recently, the derivatives 121 were used in regular organic synthesis for preparing amides from amines, but also by using weaker nucleophiles in the formation of thioesters from thiols and esters from alcohols . The preparation of more complex derivatives of 121 can be difficult, as the nucleophilicity of the indoline nitrogen is greatly reduced by delocalization through the two strong electron-withdrawing groups, but indirect routes were designed and the synthesis of a series of amino acids was recently published .…”

Synthesis of ferrocene‐based esters by alkylation of carboxylate ions and investigation of their electrochemical and optical behaviors

“…[ 30 ] Photoinduced acyl transfer and esterification also have been studied in state‐of‐the‐art. [ 31 ] The Baylis–Hillman adducts have also been adopted for ester synthesis. [ 32 ] Green chemical requirement led to an increase in the production of the natural esters from vegetable oil fatty acids and methanol to prepare the corresponding methyl ester, and consequently, reaction with other alcohols with acidic or basic catalysis is used to obtain triesters.…”

Towards a Photochemical Synthesis of Peptides

“…[12] Early candidates were amidopyridine derivatives such as 1 (Scheme 1). [13] Paralleling the structurally related photo-Fries rearrangement (which is well known on phenol esters), we banked on a photoinduced migration of the acyl group to the pyridine-type nitrogen atom, leading to an intermediate reminiscent of the DMAP-accelerated acylation of alcohols.…”