An Update of Transition Metal-Catalyzed Decarboxylative Transformations of Cyclic Carbonates and Carbamates

Molecules, Journal Year: 2019, Volume and Issue: 24(21), P. 3930 - 3930

Published: Oct. 31, 2019

Functionalized cyclic organic carbonates and carbamates are frequently used in a number of transition metal-catalyzed decarboxylative reactions for the construction interesting molecules. These transformations have attracted more research attention recent years mainly due to their advantages less waste generation versatile reactivities. On basis previous reviews on this hot topic, present review will focus development functionalized last two years.

Language: Английский

---

Regio‐ and Enantioselective Synthesis of Sulfone‐Bearing Quaternary Carbon Stereocenters by Pd‐Catalyzed Allylic Substitution

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(3), P. 1340 - 1345

Published: Sept. 10, 2019

Abstract Chiral sulfones are of great importance in medicinal chemistry and chemical synthesis. Efficient methods for preparing enantiomerically enriched sulfone‐containing molecules can therefore be significant value; such methods, however, uncommon. Herein, we report the first general palladium‐catalyzed sulfonylation vinyl cyclic carbonates with sodium sulfinates. A series tertiary allylic were synthesized good yields excellent enantiomeric ratios. Both aliphatic‐ aryl‐substituted suitable reactants results. This reaction features broad substrates scope, readily available starting materials, regio‐ enantioselectivity, synthesis sulfone‐bearing quaternary carbon stereocenters. Through geranyl derived carbonate 1 h , achieve formal total (+)‐agelasidine A.

Language: Английский

---

Palladium-catalysed decarboxylative annulations of vinylethylene carbonates leading to diverse functionalised heterocycles

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(19), P. 3638 - 3648

Published: Jan. 1, 2020

This review provides an overview of the palladium-catalysed diverse cyclisations VECs over past five years, which could offer powerful synthetic tools to access various functionalised heterocycles.

Language: Английский

---

Diastereoselective Construction of 6,8-Dioxabicyclo[3.2.1]octane Frameworks from Vinylethylene Carbonates via Palladium-Organo Relay Catalysis

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(9), P. 8256 - 8262

Published: July 29, 2019

The 6,8-dioxabicyclo[3.2.1]octane (6,8-DOBCO) architecture widely exists in a broad spectrum of bioactive natural products, and the development efficient convenient protocols to construct this skeleton remains challenging task. Here, we report concise synthetic strategy for single-step construction 6,8-DOBCO frameworks from simple vinylethylene carbonates amine-substituted enones. This protocol features sequential reaction N-allylic substitution, Diels–Alder cyclization, intramolecular ketalization, which is promoted by metal-organo relay catalysis involving palladium/phosphoric acid or palladium/halogen-bonding catalytic system. Over 50 examples derivatives with structural diversity have been facilely achieved satisfactory results, including high levels stereoselectivity, reasonable isolated yield, ample scope partners, step economy, operational simplicity.

Language: Английский

---

Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates

Catalysts, Journal Year: 2020, Volume and Issue: 10(11), P. 1339 - 1339

Published: Nov. 17, 2020

The construction of a C-S bond is powerful strategy for the synthesis sulfur containing compounds including sulfides, sulfoxides, and sulfones. Recent methodological developments have revealed lots novel protocols formation, providing easy access to compounds. Unlike traditional Ullmann typed coupling reaction, recently developed reactions frequently use non-halide compounds, such as diazo simple arenes/alkanes instead aryl halides substrates. On other hand, reaction pathways involving thiyl radicals emerged an important construct bonds. In this review, we focus on recent advances sulfones from substrates construction.

Language: Английский

---

Synergistic Pd/Cu catalysis for stereoselective allylation of vinylethylene carbonates with glycine iminoesters: Enantioselective access to diverse trisubstituted allylic amino acid derivatives

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 228 - 232

Published: April 19, 2021

We reported a synergistic Pd/Cu catalyzed enantioselective decarboxylative allylation of vinylethylene carbonates with glycine iminoesters, which provides facile access to non-proteinogenic diverse trisubstituted allylic amino acid derivatives in high yields, exclusive regioselectivities and excellent stereoselectivities. This reaction tolerates wide range γ β-aryl substituted either electron-donating or electron-withdrawing groups. Significantly, this method was proven be sufficient the gram scale synthesis chiral while retaining enantioselectivity geometric control.

Language: Английский

---

Recent applications of vinylethylene carbonates in Pd-catalyzed allylic substitution and annulation reactions: Synthesis of multifunctional allylic and cyclic structural motifs

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 462, P. 214526 - 214526

Published: March 30, 2022

Language: Английский

---

Vinylethylene Carbonates as α,β-Unsaturated Aldehyde Surrogates for Regioselective [3 + 3] Cycloaddition

Organic Letters, Journal Year: 2019, Volume and Issue: 21(17), P. 6674 - 6678

Published: Aug. 9, 2019

Herein, we report a novel stepwise addition-controlled ring size method, to access tetrahydropyrimidines through an operationally simple [3 + 3] cycloaddition of vinylethylene carbonates with triazinanes. Interestingly, could also use this method for oxidative cycloaddition, which allows the facile synthesis polysubstituted terphenyls under mild conditions. Mechanistic studies suggest that generate α,β-unsaturated aldehydes as 3-carbon synthons via combination process Pd-catalyzed decarboxylation and β-H elimination.

Language: Английский

---

Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(22), P. 9982 - 9992

Published: April 30, 2020

The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional represents a great challenge in organic synthesis. Herein, we wish to report distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables direct coupling diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or benzoxazinones afford alcohol-, amine-, aniline-containing 1,3-dienes moderate high yields excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, broad substrate scope, gram-scalability. Notably, structurally unique allylic Pd(II) intermediate was isolated characterized. DFT calculation control experiments demonstrated rare carbene could be involved this reaction. Moreover, butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited P-glycoprotein dramatically reversed multidrug resistance cancer cells by 190-fold.

Language: Английский

---

A modular biomimetic strategy for the synthesis of macrolide P-glycoprotein inhibitors via Rh-catalyzed C-H activation

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: May 1, 2020

Abstract One of the key challenges to overcome multidrug resistance (MDR) in cancer is development more effective and general strategies discover bioactive scaffolds. Inspired by natural products, we describe a strategy achieve this goal modular biomimetic synthesis scaffolds ( Z )-allylic-supported macrolides. Herein, an Rh(III)-catalyzed native carboxylic acid-directed solvent-free C−H activation allylation with high stereoselectivity chemoselectivity achieved. The generated poly-substituted allylic alcohol as multifunctional building block crucial for Moreover, unique allylic-supported macrolides significantly potentiate sensitivity tumor cells cytotoxic agents such vinorelbine doxetaxel reversing p170-glycoprotein-mediated MDR. Our findings will inspire evolution synthetic chemistry open avenues expedient diversified macrocyclic molecules.

Language: Английский

---