Metal‐Catalyzed Synthesis and Use of Thioesters: Recent Developments

Abstract

While thioesters are common intermediates in biochemical processes, they are much less appreciated in organic synthesis, also compared to other carboxylic acid derivatives. However, their chemistry and reactivity is intriguing and diversified, reaching much further than the acyl substitution and aldol chemistry. Herein, we focus on metal-catalyzed reactions for the synthesis of thioesters as well as their transformations. Reactions such as thiocarbonylation, cross-coupling, decarbonylation, allylic substitution or dual photoredox/metal catalysis are discussed. On one hand, new atom economic methods allow for convenient synthesis of thioesters from well available starting materials. On the other hand, various synthetically important compounds can by synthesized due to the multifaceted reactivity of thioesters that we aimed to depict.

Catalytic C−H/C−F Coupling of Azoles and Acyl Fluorides

“…Transition‐metal‐catalyzed cross‐coupling reactions of acyl electrophiles with aryl nucleophiles represent a powerful and reliable synthetic strategy for the introduction of acyl fragments into aromatic rings to provide aromatic ketones, and a large variety of carboxylic acid derivatives are currently used as acyl electrophiles . Among these, acyl fluorides have recently gained much attention as valuable carbon‐based electrophiles in cross‐coupling reactions, especially in acyl coupling and decarbonylative coupling reactions .…”

“…Transition-metal-catalyzed cross-couplingreactions of acyl electrophiles with aryl nucleophilesr epresent ap owerful and reliable synthetic strategy for the introductiono fa cyl fragments into aromatic rings to provide aromatick etones, and al arge variety of carboxylic acid derivatives are currently used as acyl electrophiles. [1][2][3][4][5][6][7][8][9][10][11][12][13] Amongt hese, acyl fluorides have recently gained much attention as valuablec arbon-based electrophiles in cross-couplingreactions, especially in acyl coupling [14][15][16][17] and decarbonylative coupling reactions. [17][18][19][20][21][22] Due to the moderate electrophilicity of acyl fluorides,t hey exhibit ag ood balance between stability and reactivity with respectt ot heir compatibility under nucleophilic conditions, that is, they are more stable than the commonly employed acyl chlorides, [4] yet more reactive than the corresponding esters [9, 13b] and amides.…”

Thioester synthesis through geoelectrochemical CO2 fixation on Ni sulfides

“…Thioesters are versatile compounds in organic chemical synthesis as well as in biosynthesis, enabling diverse coupling reactions including C-C bond formation, esterification, and amide bond formation owing to the activated acyl unit. [21][22][23] To the best of our knowledge, our study provides the first experimental demonstration of thioester synthesis from CO and thiol under mild aqueous condition. Thus, besides rendering a realistic support for autotrophic scenarios of the origin of life, [2,3] our demonstrated COthiol reaction on NiS_PERM could be a practical approach to CO utilization.…”

Solvent Dependent Divergent Reactivity of Electron‐Rich Dienones with and without Visible Light: Access to Cyclopropanated Furans and Butenolides

“…It is also evident from the results that protic solvent is unique in generating O 2 À in comparison to the other solvents and also preventing the formation of singlet oxygen. This is not unexpected as the oxoester is less reactive towards nucleophiles than a thioester [23] and the poor nucleophilicity of the oxygen atom hinders subsequent oxygen migration after intramolecular lactonization (Table 4). Subsequent 5-exo-trig radical cyclization of II would provide the distal radical cation III.…”