Vinyl and Aryl Sulfonates: Preparations and Applications in Total Synthesis

Abstract

Vinyl and aryl sulfonates are ubiquitous building blocks in organic chemistry, frequently exploited in the total synthesis of natural and non-natural products, due to their ease of formation and to their high reactivity, especially in metal-catalyzed cross-coupling reactions. The present review thus aims at first describing the classical and current methods to prepare these valuable synthons, with an emphasis on reaction mechanisms. The second part of the review aims at highlighting their main applications in organic synthesis, especially in the course of natural product total syntheses.

Homolytic C–O Cleavage in Phosphates and Sulfonates

“…The activation of the C–O bond is possibly the most common chemical process, which is widely used in industrial and medicinal chemistry. − Recently, there has been increasing interest in cross-coupling reactions of phosphates , and sulfonates, , which can be easily synthesized from abundant and inexpensive carbonyl and phenol derivatives; − and the C–C bonds can be formed through the activation of C–O bonds. For instance, Chen et al successfully developed Suzuki-Miyaura cross-coupling of aryl phosphates with organoboron reagent using the best precatalyst of [NiCl 2 (Pcy 3 ) 2 ], which is inexpensive and bench-stable (Scheme ).…”

General Synthesis of Alkenyl Sulfides by Palladium-Catalyzed Thioetherification of Alkenyl Halides and Tosylates

“…Among sulfonates, alkenyl tosylates are more convenient counterparts than the corresponding triflates because of the lower cost of the sulfonating reagents used for their preparation, as well as their greater crystallinity and stability to water, which allows their storage. 15 However, this stability makes the oxidative addition to Pd(0) more challenging and, therefore, alkenyl tosylates are less reactive in palladium-catalyzed processes. 16 Consequently, couplings of alkenyl tosylates with thiols are unknown.…”

“…Alkenyl sulfonates are attractive alternatives to halides, as they are easily synthesized from abundantly available ketones and increase the range of available substitution patterns. Among sulfonates, alkenyl tosylates are more convenient counterparts than the corresponding triflates because of the lower cost of the sulfonating reagents used for their preparation, as well as their greater crystallinity and stability to water, which allows their storage . However, this stability makes the oxidative addition to Pd(0) more challenging, and therefore, alkenyl tosylates are less reactive in palladium-catalyzed processes .…”

Electrochemical multi-component reaction of potassium metabisulfite with alkenes and alcohols enabling synthesis of sulfonate esters

“…4 On the other hand, sulfonate esters also belong to useful synthetic building blocks in organic chemistry as they are good leaving groups and could be widely used in cross-coupling and substitution reactions. 5,6 The synthetic methods for sulfonate esters have usually focused on the esterification of active sulfonyl reagents, such as sulfonyl chlorides and sulfonic anhydrides, in the presence of bases. 7 Although there were some other strategies also developed in recent years, 8,9 these methods usually need harsh conditions, hazardous reagents, or transition-metal catalysts.…”