Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(14), P. 8701 - 8780

Published: June 25, 2019

Organosulfur compounds have long played a vital role in organic chemistry and the development of novel chemical structures architectures. Prominent among these organosulfur are those involving sulfur(IV) center, which been subject countless investigations over more than hundred years. In addition to list textbook sulfur-based reactions, there has sustained interest organosulfur(IV) recent Of particular within is ease with synthetic chemist can effect wide range transformations through either bond formation or cleavage at sulfur. This review aims cover developments past decade molecules provide insight into both reactions critically rely on this versatile element diverse scaffolds that thereby be synthesized.

Language: Английский

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Chiral Amino Acids‐Derived Catalysts and Ligands

Chinese Journal of Chemistry, Journal Year: 2018, Volume and Issue: 36(9), P. 791 - 797

Published: May 23, 2018

Abstract Transforming amino acids into novel catalysts and ligands is a remarkable subset of new catalyst development in order to imitate enzymatic efficiencies. Their ability perform variety asymmetric catalytic reactions complimented by their ready availability, rich transformations, stability easy procedure. Herein, we focused on describing our endeavor developing from primary secondary acids. It includes C 2 ‐symmetric N , N' ‐dioxides, guanidine‐amides, bispidine‐based diamines, other organic salts. The account covered brief introduction about discovery, representative applications related mechanisms.

Language: Английский

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Asymmetric Catalytic Rearrangements with α-Diazocarbonyl Compounds

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(3), P. 415 - 428

Published: Jan. 14, 2022

Conspectusα-Diazocarbonyl compounds serve as nucleophiles, dipoles, carbene precursors, and rare electrophiles, enabling a vast array of organic transformations under the influence metal catalysts. Among them, rearrangement processes are attractive provide straightforward efficient accesses to one-carbon extension adducts or heteroatom-containing molecules. The reactions occur upon release dinitrogen after nucleophilic addition before ylide formation. Although significant progress has been made for these two types reactions, issue enantiocontrol is challenging because final optically enriched products generated via multistep inherent spacial arrangement intermediates more less on regio- enantioselectivity.In this Account, we collected several rearrangements α-diazocarbonyl compounds, showcasing catalysts tailored strategies tackling enantioselective varieties reactions. Our research group initiated catalytic asymmetric during development chiral Feng N,N′-dioxide–metal complex others. As kind useful Lewis acid catalyst complexes favorable activation various carbonyl accelerating diastereo- α-diazoesters sequential in either an intermolecular intramolecular manner. Aldehydes, acyclic cyclic ketone derivatives, α,β-unsaturated ketones could participate homologation obvious ligand-acceleration effect observed processes. For example, Roskamp–Feng reaction aldehydes gives active β-ketoesters through H-shift, overwhelming aryl shift oxygen attack. preference derivatives be excellent control An unusual electrophilic α-amination aryl/alkyl even complicated homologation/dyotropic rearrangement/interconversion/[3 + 2] cycloaddition cascade used construct dimeric polycyclic were discovered result selection ligands additives. On basis understanding interaction functional with catalysis key enantio-determining issues ylide-based rearrangements, designed new by introducing pyrazole-1-carboxyl acceptor unit, which benefit formation both carbenoid species catalyst-bound ylides deliver stereoselectivity. Taking advantage Ni(II) Co(II) N,N′-dioxide ligands, realized kinds [2,3]-sigmatropic such Doyle–Kirmse allylic sulfides selenides, [2,3]-Stevens vinyl-substituted α-diazo pyrazoleamides thioacetates, Sommelet–Hauser aryl-substituted thioamides, thio-Claisen 2-thio-indoles well. Moreover, strategy was shown applicable highly γ-selective insertion into N–H bonds secondary amines pyrazoleamides.

Language: Английский

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Recent Perspectives on Rearrangement Reactions of Ylides via Carbene Transfer Reactions

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(4), P. 1270 - 1281

Published: Aug. 5, 2020

Abstract Among the available methods to increase molecular complexity, sigmatropic rearrangements occupy a distinct position in organic synthesis. Despite being known for over century rearrangement reactions of ylides via carbene transfer reaction have only recently come age. Most ylide mediated processes involve rupture σ‐bond and formation new bond between π‐bond negatively charged atom followed by simultaneous redistribution π‐electrons. This minireview describes advances this research area made recent years, which now opens up metal‐catalyzed enantioselective reactions, metal‐free photochemical novel pathways that can be accessed intermediates.

Language: Английский

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Prospects and Challenges in Organosulfur Chemistry

ACS Sustainable Chemistry & Engineering, Journal Year: 2022, Volume and Issue: 10(2), P. 671 - 677

Published: Jan. 3, 2022

Sulfur-containing molecules are increasingly crucial in chemistry-related fields and widely applied life science, material food pharmaceutical science. This perspective focuses on the introduction of green sulfurizing reagents sustainable methodologies to realize diverse kinds functionalized transformations synthetic applications. The text is organized according structure sulfur-containing corresponding method. It expected be interest organic chemistry professionals who wish better understand insights applications organosulfur transformations.

Language: Английский

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Asymmetric Catalytic [2,3] Stevens and Sommelet–Hauser Rearrangements of α‐Diazo Pyrazoleamides with Sulfides

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(38), P. 13492 - 13498

Published: July 23, 2019

Abstract Catalytic enantioselective [2,3] Stevens and Sommelet–Hauser rearrangements of α‐diazo pyrazoleamides with sulfides were achieved by utilizing chiral N , ′‐dioxide/nickel( II ) complex catalysts. These proceeded well under mild reaction conditions, providing rapid facile access to a series functionalized 1,6‐dicarbonyls or sulfane‐substituted phenylacetates high excellent enantioselectivities. The catalytic system shows stereocontrol, discriminating between the heterotopic lone pairs sulfur controlling both 1,3‐proton transfer [2,3]‐σ rearrangement.

Language: Английский

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A leap forward in sulfonium salt and sulfur ylide chemistry

Chinese Chemical Letters, Journal Year: 2020, Volume and Issue: 32(1), P. 299 - 312

Published: June 3, 2020

Language: Английский

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Feng Ligand: Privileged Chiral Ligand in Asymmetric Catalysis

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 39(4), P. 969 - 984

Published: Nov. 18, 2020

Abstract Catalysts and ligands possessing the great ability to tolerate over a wide range of mechanistically unrelated reactions are remarked as "privileged", which rather scarce but extremely meaningful in asymmetric catalysis. Feng co‐workers have developed library conformationally flexible, C 2 ‐symmetric N,N '‐dioxide amide compounds with original design featured structure (named ligand now). They were initially reported chiral organocatalysts 2005 been further new class privileged since 2006. Tremendous success, including versatile coordination chemistry plenty metal sources (main‐group metals, transition rare‐earth metals), truly broad scope (more than 50 types), diverse areas catalysis (organocatalysis, Lewis‐acid catalysis, bimetallic relay photocatalysis), numerous synthetic applications bioactive compounds, has achieved using N , '‐dioxide. Besides, they demonstrate that flexible property can offer excellent environment well, challenges conventional idea preferring rigid structures ligands. Herein, we briefly introduced discovery millstones during development. We also covered successful by other scientists well novel inspired them.

Language: Английский

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Copper‐Catalyzed Asymmetric Diyne Cyclization via [1,2]‐Stevens‐Type Rearrangement for the Synthesis of Chiral Chromeno[3,4‐c]pyrroles

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(7)

Published: Dec. 14, 2021

Here, we report a copper-catalyzed asymmetric cascade cyclization/[1,2]-Stevens-type rearrangement via non-diazo approach, leading to the practical and atom-economic assembly of various valuable chiral chromeno[3,4-c]pyrroles bearing quaternary carbon stereocenter in generally moderate good yields with wide substrate scope excellent enantioselectivities (up 99 % ee). Importantly, this protocol not only represents first example catalytic [1,2]-Stevens-type based on alkynes but also constitutes formal carbene insertion into Si-O bond.

Language: Английский

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Enantioselective Formal Vinylogous N–H Insertion of Secondary Aliphatic Amines Catalyzed by a High-Spin Cobalt(II) Complex

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(25), P. 9648 - 9656

Published: June 21, 2021

Vinylcarbene insertion into the nitrogen–hydrogen (N–H) bond of amines allows direct access to α,β-unsaturated γ-amino acid derivatives, meeting a marked challenge in control regio- and enantioselectivities. Here, we report highly γ-selective enantioselective N–H bonds aliphatic or aromatic secondary with vinyl substituted α-diazo pyrazoleamides using high-spin chiral N,N′-dioxide/cobalt(II) complex catalyst. The method affords wide variety valuable optically active Z- E-type amides. Calculation reveals spin state change from quartet cobalt(II) doublet Co(II)-carbene species for facile Z-selective nucleophilic addition.

Language: Английский

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