Photocatalytic Carboxylation of C−N Bonds in Cyclic Amines with CO₂ by Consecutive Visible‐Light‐Induced Electron Transfer

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 21, 2023

Abstract Visible‐light photocatalytic carboxylation with CO 2 is highly important. However, it still remains challenging for reluctant substrates low reduction potentials. Herein, we report a novel of C−N bonds in cyclic amines via consecutive photo‐induced electron transfer (ConPET). It also the first reductive ring‐opening reaction azetidines, pyrrolidines and piperidines. This strategy practical to transform variety easily available valuable β‐, γ‐, δ‐ ϵ‐amino acids moderate‐to‐excellent yields. Moreover, method features mild transition‐metal‐free conditions, high selectivity, good functional‐group tolerance, facile scalability product derivations. Mechanistic studies indicate that ConPET might be key generating reactive photocatalysts, which enable activation generate carbon radicals carbanions as intermediates.

Language: Английский

---

Visible-light-driven synthesis of N-heteroaromatic carboxylic acids by thiolate-catalysed carboxylation of C(sp²)–H bonds using CO2

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(3), P. 394 - 405

Published: Jan. 11, 2024

Language: Английский

---

Visible-Light Photoredox-Catalyzed Intermolecular α-Aminomethyl/Carboxylative Dearomatization of Indoles with CO₂ and α-Aminoalkyl Radical Precursors

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 467 - 472

Published: Jan. 5, 2024

Disclosed here is a visible-light photoredox-catalyzed intermolecular sequential α-aminomethyl/carboxylative dearomatization of indoles with CO2 and α-aminoalkyl radical precursors, affording series functionalized indoline-3-carboxylic acids lactams in good yields high regioselectivity. This multicomponent reaction provides green facile method for the synthesis diverse indolines by using as carboxylic carbonyl source.

Language: Английский

---

Kinetically-Controlled Ni-Catalyzed Direct Carboxylation of Unactivated Secondary Alkyl Bromides without Chain Walking

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1753 - 1759

Published: Jan. 9, 2024

Herein, we report the direct carboxylation of unactivated secondary alkyl bromides enabled by merger photoredox and nickel catalysis, a previously inaccessible endeavor in arena. Site-selectivity is dictated kinetically controlled insertion CO2 at initial C(sp3)–Br site rapid formation Ni(I)–alkyl species, thus avoiding undesired β-hydride elimination chain-walking processes. Preliminary mechanistic experiments reveal subtleties stereoelectronic effects for guiding reactivity site-selectivity.

Language: Английский

---

Combination of dimensional reduction and active site addition strategies for preparing unique {RE₉}-cluster-based MOFs: efficient CO₂ fixation and Knoevenagel condensation

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2071 - 2080

Published: Jan. 1, 2024

A series of 2D {RE 9 }-cluster-based rare-earth MOFs were built by dimensional reduction and active site addition strategies. They exhibit excellent catalytic activity in CO 2 fixation Knoevenagel condensation under mild conditions.

Language: Английский

---