Recent Advances in Decarboxylative Conversions of Cyclic Carbonates and Beyond

Abstract

Functionalized cyclic organic carbonates have emerged as valuable building blocks for the construction of interesting and useful molecules upon decarboxylation under transition metal catalysis in recent years. With suitable catalytic system, the development of chemo-, regio-, stereo- and enantioselective methods for the synthesis of useful and interesting compounds has advanced greatly. On the basis of previous research work on this topic, this short review will highlight the synthetic potential of cyclic carbonates under transition metal catalysis in last two years. 1 Introduction 2 Transition metal catalyzed decarboxylation of vinyl cyclic carbonates 3 Zwitterionic enolate chemistry based on transition metal catalysis 4 Decarboxylation of alkynyl cyclic carbonates and dioxazolones 5 Conclusions and perspectives

Advancement of vinylene carbonate as a coupling partner in metal-catalyzed C–H functionalization

“…In addition, other functionalized cyclic organic carbonates have also evolved into diversified appealing coupling partners in modern organic synthesis. 10–13 Generally, these five or six-membered saturated cyclic organic carbonates generate interesting zwitterionic intermediates upon decarboxylation under transition-metal (TM) catalysis, 14–17 and the remaining fragments further react with electrophiles or nucleophiles to delivery linear or cyclic products (Fig. 1).…”

Pd-catalyzed exclusively regioselective [5 + 4] cycloaddition for the construction of 1,5-di/ox-azonanes

“…[5 + 4] cycloaddition, as an efficient and flexible approach, provides a significant advantage of directly coupling two building blocks (serving as dipoles and dipolarophiles) to produce nine-membered heterocycles. 5–21 In 2017, the Zhao group 5,6 reported the first [5 + 4] cycloaddition between α,β-unsaturated imines and vinylethylene carbonates (VECs) for the construction of nine-membered heterocycles via palladium catalysis. Since then, a series of excellent studies about palladium-catalyzed [5 + 4] cycloaddition involving 1,5-dipoles and α,β-unsaturated imines have been reported by Zhao, 8,14 Archambeau, 15 Guo, 16 Hu 17,18 and Li 21 groups.…”

Palladium-Catalyzed Asymmetric (3 + 2) Cycloaddition of 5-Allenyloxazolidine-2,4-Diones with Barbiturate-Derived Alkenes: Synthesis of Spirobarbiturate-γ-Lactams

“…Cycloaddition of π-allyl palladium zwitterions is a powerful tool for constructing ring structures and has been extensively investigated over the past decade . To date, various precursors for generating the π-allyl palladium zwitterions have been developed, such as vinyl cyclic carbonates, vinyl methylene cyclic carbonates, vinyl cyclic carbamates, vinyl lactones, methylidene cyclic carbonates, methylidene cyclic carbamates, methylidene lactones, and acyclic carbonates .…”