Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones

Abstract

Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation of at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is of great interest to chemists that this type of cycloaddition reactions possesses some special advantages such as high reactivity, exclusive regioselectivity, and good functional group compatibility. Based on these qualities, palladium‐catalyzed decarboxylative cycloadditions present strong ability in synthetic chemistry and have been flourished especially in the last five years. In this review, the achievements in palladium‐catalyzed decarboxylative cycloadditions involving cyclic carbonates, carbamates, and lactones for accessing oxacyclo‐, azacyclo‐ and carbocyclic compounds are addressed. Mechanistic insights and some synthetic applications toward the synthesis of natural products are discussed. The challenges and opportunities of this field are also outlined.

Pd-Catalyzed Tandem [5 + 2] Cycloaddition/Ring Contraction of Phthalide-Derived Alkenes and Vinylethylene Carbonates for the Construction of Benzo-[5,5]-spiroketal Lactones

“…In recent years, vinylethylene carbonates (VECs) have been shown to be versatile and robust building blocks, especially in the synthesis of oxygen-containing heterocycles via palladium-catalyzed cycloadditions . Among them, even catalytic asymmetric [3 + 2] cycloadditions of VECs and di- or trisubstituted electron-deficient alkenes have drawn much attention for their capacity on the construction of structurally complex tetrahydrofurans .…”

Recent Progress in Heterocycle Synthesis: Cyclization Reaction with Pyridinium and Quinolinium 1,4-Zwitterions

“…The transition-metal-catalyzed decarboxylative cyclization of alkyne-substituted carbonates has emerged as an effective strategy for the construction of various heterocycles [ 87 , 88 , 89 , 90 ]. In 2022, Yuan et al described a copper-catalyzed decarboxylative cascade cyclization of propargylic cyclic carbonates 120 /carbamates 121 with pyridinium 1,4-zwitterions 1 ( Scheme 27 ) [ 91 ].…”

Palladium-catalyzed stereoselective decarboxylative allylation of azlactones: access to (Z)-trisubstituted allylic amino acid derivatives

“…Transition metal-catalyzed decarboxylative transformation has become a powerful and versatile synthetic strategy for generating diverse structural motifs containing the carbon–carbon double bond, and aroused a wide range of research interests due to some advantages, such as easy operation, redox neutrality, and only CO 2 -byproduct generation. 7 Among them, palladium-catalyzed decarboxylative allylic substitution of vinylethylene carbonates, which is exemplified by using suitable nucleophiles attacking the in situ generated highly reactive Pd–allyl intermediates, offers a feasible approach to access different and important allyl-containing compounds. 8 In this aspect, vinyl methylene cyclic carbonates (VMCCs), a new type of Pd–allyl species precursor, were designed and used in a cycloaddition reaction by the group of Zi and Guo in 2021, respectively (Scheme 1).…”