Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Abstract

Herein, we highlight advances in the phosphorylation of readily available carboxylic acids and their derivatives forming synthetically important P(O)–sp3C, P(O)–sp2C, and P(O)–spC bonds, with an emphasis on the results demonstrated since 2010. This review examines the challenges associated with the use of this strategy for the synthesis of organophosphorus compounds and details advances in the design of catalytic systems that suppress these problems thus resulting in notable progress. Mechanistic details are discussed where available.1 Introduction2 Formation of P(O)–sp3C Bonds3 Formation of P(O)–sp2C Bonds4 Formation of P(O)–spC Bonds5 Outlook and Conclusion

Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C–F Bond Activation

“…Besides, once 4h was isolated and subjected to the standard reaction conditions of this study, the target product 3h was obtained in 81% yield (Scheme 4b). This result is consistent with the report by Rueping on the synthesis of sulfides from thioesters 18 by a similar nickel-catalyzed decarbonylation reaction. 7g Based on the results of the relevant mechanistic studies obtained above, the catalytic cycle for this reaction is proposed as shown in Scheme 5.…”

Photocatalyzed Dowd–Beckwith radical-polar crossover reaction for the synthesis of medium-sized carbocyclic compounds

“…Recently, numerous research groups have found that redox-active esters are more reactive than alkyl iodides and provide alkyl radicals via single-electron reduction followed by decarboxylation with the release of a non-nucleophilic leaving group. 11 Pleasingly, irradiation of 1a ( E 1/2 = −1.23 V vs. SCE of 1a) 10 in MeOH provided the desired ring-expansion product 2a with 40% yield ( Scheme 2 ). 12 A substantial increase in the reaction yield was observed by employing more reducing photocatalysts, probably due to the more favourable single-electron transfer between the excited state Ir III and redox-active ester 1a ( Table 1 , entries 2–4).…”