Generation and transformation of α-oxy carbene intermediates enabled by copper-catalyzed carbonylation

Green Carbon, Journal Year: 2024, Volume and Issue: 2(1), P. 70 - 80

Published: Jan. 11, 2024

Since the Fischer-Tropsch reaction was discovered by Otto Roelen in 1938, transition metal-catalyzed carbonylation reactions come as one of most important methods for preparing carbonyl-containing and carbon chain-increased compounds. As a result, field research has received considerable attention over past decades continues to increase. With continuous development in-depth study mechanism, more mechanistic details variations have been revealed, which provide possibilities organic synthesis. Recently, copper catalysis introduced carbonylative functionalization alkenes, thus enabling rapid assembly functionalized carbonyl compounds from simple starting materials. In this Account, we summarize new findings Cu-catalyzed borocarbonylation alkenes based on generation transformation α-oxy carbene intermediates. We believe that results presented Account will further inspire design reactions.

Language: Английский

---

Visible-Light-Mediated Formal Carbene Insertion Reaction: Enantioselective Synthesis of 1,4-Dicarbonyl Compounds Containing All-Carbon Quaternary Stereocenter

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(9), P. 5510 - 5516

Published: April 25, 2022

We developed an efficient visible-light-mediated formal carbene insertion reaction of 1,3-diketones with diazoesters for the construction enantioenriched 1,4-dicarbonyl compounds a quaternary carbon center. Combining visible light and Brønsted acid catalyst, chiral were achieved in good yields high enantioselectivities by photochemical transfer protocol.

Language: Английский

---

Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(4)

Published: March 23, 2022

Abstract In recent years, the transition‐metal‐catalyzed functionalization reactions of sulfoxonium ylides have been explored extensively because their usefulness as carbene‐transfer agents, since they can produce metal carbenes through catalysis. Moreover, are safer and advantages simple handling good stability over other counterparts like diazo‐compounds. This review article attempts to highlight advances in metal‐catalyzed C−H ylides.

Language: Английский

---

Enantioselective α-Boryl Carbene Transformations

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9871 - 9879

Published: March 28, 2024

Carbenes, recognized as potent intermediates, enable unique chemical transformations, and organoborons are pivotal in diverse applications. As a hybrid of carbene the boryl group, α-boryl carbenes promising intermediates for construction organoborons; unfortunately, such hard to access have low structural diversity with their asymmetric transformations largely uncharted. In this research, we utilized cyclopropenes precursors swift synthesis metal carbenes, powerful category chiral organoboron synthesis. These undergo series highly enantioselective transfer reactions, including B–H Si–H insertion, cyclopropanation, cyclopropanation/Cope rearrangement, catalyzed by singular copper complex. This approach opens paths previously unattainable but easily transformable organoborons, expanding both chemistry.

Language: Английский

---

Deoxygenative Cross‐Coupling of Aromatic Amides with Polyfluoroarenes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(11)

Published: Jan. 11, 2022

Abstract Considering the ubiquitous nature and ready synthesis of amides, great significance organofluorine‐containing species, cross‐coupling amides polyfluoroarenes, leading to new carbon–carbon bond‐forming methodologies, would find useful applications in synthesis, late‐stage functionalization, rapid generation molecular diversity. Herein, we present a novel α‐polyfluoroaryl amines via Sm/SmI 2 ‐mediated deoxygenative aromatic with polyfluoroarenes through direct C−H functionalization. The structural functional diversity these readily available precursors provides versatile flexible strategy for streamlined amines. Combining experimental theoretical studies, plausible mechanism α‐aminocarbene‐mediated insertion has been revealed, which may stimulate future work development methods amine synthesis.

Language: Английский

---

Highly Regio‐, Stereo‐, and Enantioselective Copper‐Catalyzed B−H Bond Insertion of α‐Silylcarbenes: Efficient Access to Chiral Allylic gem‐Silylboranes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(26)

Published: April 19, 2022

Herein, we report the development of a method for highly regio-, stereo-, and enantioselective B-H bond insertion reactions α-silylcarbenes generated from 1-silylcyclopropenes in presence chiral copper(I)/bisoxazoline catalyst construction γ,γ-disubstituted allylic gem-silylboranes, which cannot be prepared by any other known methods. This reaction is first carbene ever to reported. The shows general applicability various 3,3-disubstituted silylcyclopropenes exclusively affords E-products. novel gem-silylborane products are versatile bimetallic reagents with high stability have great synthetic potential, especially complex molecules continuous centers.

Language: Английский

---

Dirhodium: carbene transformations and beyond

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2849 - 2878

Published: Jan. 1, 2023

Dirhodium-catalyzed transformations, not limited to carbene and nitrene transfer reactions, are reviewed, including cycloisomerization, hetero-Diels–Alder (HDA) ene arylation, radical oxidation reactions C–H activation, etc .

Language: Английский

---

Enantioselective Photochemical Carbene Insertion into C–C and C–H Bonds of 1,3-Diketones by a Guanidine-Amide Organocatalyst

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4656 - 4666

Published: March 22, 2023

A visible-light-induced enantioselective free carbene transfer reaction of α-diazoesters with 1,3-diketones is established by utilizing a chiral bifunctional guanidine-amide organocatalyst. Selective insertion into the C–C or C–H bonds 1,3-diketone could be achieved bearing different steric hindrances. The transformations enable preparation series 1,4-diketones quaternary carbon center 2-substituted-1,3-diketones in good enantioselectivities. On basis control experiments and DFT calculation, stepwise triplet coupling pathway suggested. possible mechanism proposed to explain origin high enantioselectivities via hydrogen-bonds electrostatic interactions catalyst.

Language: Английский

---

Metal-free cascade O–H double insertion between I^(III)/S^(VI)-ylides, carboxylic acids, and alcohols: modular access to unsymmetrical α,α-O,O-substituted ketones

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3234 - 3241

Published: Jan. 1, 2024

Herein, we present a cascade O–H double insertion reaction between I (III) /S (VI) -ylides, carboxylic acids, and alcohols under metal-free conditions, enabling the modular synthesis of unsymmetrical α,α- O , -substituted ketones.

Language: Английский

---

Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Language: Английский

---