Dirhodium(II,II) Paddlewheel Complexes

European Journal of Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 2021(6), P. 501 - 528

Published: Jan. 7, 2021

Abstract This minireview summarizes synthetic approaches towards homoleptic dirhodium(II,II) paddlewheel complexes with the general formula Rh 2 A 4 . These have found numerous applications in a wide range of chemical research and industry as catalysts, detectors, enzymatic inhibitors or building blocks for molecular scaffolds. In organic synthesis they are commonly used to transfer electron‐deficient species, act Lewis acids activate unsaturated bonds, serve hydrogenation catalysts participate oxidation/reduction processes. Dirhodium composed Rh‐Rh backbone four bridging anions, which surround core. According application, electrochemical potential atom can be modulated, geometry physical properties metal complex. prepared one step from basic inorganic precursors by post‐functionalization structures.

Language: Английский

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Metal Bound or Free Ylides as Reaction Intermediates in Metal-Catalyzed [2,3]-Sigmatropic Rearrangements? It Depends

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(2), P. 829 - 839

Published: Jan. 4, 2021

Density functional theory calculations were applied to study four previously published metal-catalyzed [2,3]-rearrangements from onium ylide intermediates, in pursuit of generalizations about when, during these types reactions, catalysts dissociate. Our results corroborate past studies where free-ylide mechanisms proposed be operative. Results on case indicate that the origin metal–catalyst dissociation can attributed primarily steric bulkiness groups adjacent carbene carbon.

Language: Английский

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Selective [3 + 2] Cycloaddition of Cyclopropenone Derivatives and Elemental Chalcogens

Organic Letters, Journal Year: 2020, Volume and Issue: 22(14), P. 5555 - 5560

Published: July 9, 2020

A highly efficient method is disclosed for the synthesis of 1,2-dichalcogen heterocycles via [3 + 2] cycloaddition cyclopropenone derivatives and elemental chalcogens. Different from other derivatives, cyclopropenselenones undergo unprecedented rearrangement with sulfur. The features this protocol include mild reaction conditions, high efficiency, excellent atom economy, gram-scale ability, good regioselectivity.

Language: Английский

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Rhodium-catalyzed Sommelet–Hauser type rearrangement of α-diazoimines: synthesis of functionalized enamides

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(42), P. 5649 - 5652

Published: Jan. 1, 2020

An efficient rhodium catalyzed Sommelet-Hauser type rearrangement of sulfur ylides derived from α-thioesters and N-sulfonyl-1,2,3-triazoles has been successfully accomplished for the synthesis various functionalized enamides. The developed reaction involves unprecedented [2,3]-sigmatropic with imine motif. Importantly, method works well substituted α-thioesters/-amides/-ketones allows diverse enamide derivatives in good to excellent yields. was also extended one-pot enamides terminal alkynes.

Language: Английский

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Catalytic Enantioselective [4+1]-Annulation of Carboxylic Acids with Cyclopropenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

An efficient asymmetric synthesis of 3-vinylphthalides has been accomplished through rhodium-catalyzed [4+1]-annulation arylcarboxylic acids with cyclopropenes involving C–H bond functionalization. The method exhibited excellent compatibility for various functional groups and offered diverse substituted in yield enantioselectivity. Synthetic application control experiments were also performed to demonstrate the utility understand reaction pathway.

Language: Английский

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Chemoenzymatic Cascades for the Enantioselective Synthesis of β‐Hydroxysulfides Bearing a Stereocentre at the C−O or C−S Bond by Ketoreductases

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 16, 2022

Abstract Chiral β‐hydroxysulfides are an important class of organic compounds which find broad application in and pharmaceutical chemistry. Herein we describe the development novel biocatalytic chemoenzymatic methods for enantioselective synthesis by exploiting ketoreductase (KRED) enzymes. Four KREDs were discovered from a pool 384 enzymes identified isolated through metagenomic approach. KRED311 KRED349 catalysed bearing stereocentre at C−O bond with opposite absolute configurations excellent ee values biocatalytic‐chemical‐biocatalytic (bio‐chem‐bio) cascades starting commercially available thiophenols/thiols α‐haloketones/alcohols. KRED253 KRED384 C−S enantioselectivities dynamic kinetic resolution (DKR) racemic α‐thioaldehydes.

Language: Английский

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Rhodium-Catalyzed 1,4-Aryl Rearrangement of Sulfur Ylide for the Synthesis of 2-Pyridyl Thioethers

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 703 - 707

Published: Jan. 23, 2023

We report a novel rhodium-catalyzed rearrangement involving N-substituted 2-thiopyridones and diazoesters. This reaction proceeds through the formation of sulfur ylides, followed by direct C-N bond cleavage to achieve N-to-C 1,4-pyridyl migration. The protocol can be used construct various thiopyridines possessing tetrasubstituted carbon stereocenters in moderate excellent yields, which expands transformation pattern ylide intermediates reactions.

Language: Английский

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Catalytic Functionalization of Metallocarbenes Derived from α‐Diazocarbonyl Compounds and Their Precursors

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 3872 - 3883

Published: Aug. 26, 2021

Abstract Short and efficient synthesis of heterocyclic compounds are highly desirable in synthetic organic chemistry. It is a dream approach to accomplish these syntheses from readily available starting materials single step. In this personal account, we discuss our contribution the beyond N‐sulfonyl‐1,2,3‐triazoles α‐diazocarbonyl compounds, which precursors for α‐imino (carbonyl) metal carbenes presence transition catalysts. Functionalization α‐imino(carbonyl) has been achieved through in‐situ generated metal‐stabilized ylides followed by either intramolecular trapping non‐polar bonds, rearrangement, cycloaddition, or 1,3‐insertion fashion, led various synthetically important intermediates compounds.

Language: Английский

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An Umpolung Oxa-[2,3] Sigmatropic Rearrangement Employing Arynes for the Synthesis of Functionalized Enol Ethers

Organic Letters, Journal Year: 2021, Volume and Issue: 23(9), P. 3447 - 3452

Published: April 8, 2021

An oxa-[2,3] sigmatropic rearrangement involving arynes is reported featuring the umpolung of ketones, where C═O bond polarity reversed. The in situ-generated sulfur ylides from β-keto thioethers and undergo efficient allowing facile robust synthesis functionalized enol ethers high yields excellent functional group compatibility. Preliminary mechanistic studies rule out possibility Pummerer-type operating this case.

Language: Английский

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Selenonium Ylides: Syntheses, Structural Aspects, and Synthetic Applications

Molecules, Journal Year: 2020, Volume and Issue: 25(10), P. 2420 - 2420

Published: May 22, 2020

The goals of this mini review constitute (a) a presentation the synthetic protocols applied to preparation achiral and non-racemic selenonium ylides; (b) discussion their basic structural features, including optical activity; (c) description applications in general methodology asymmetric synthesis.

Language: Английский

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