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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Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(10), P. 4578 - 4611

Published: April 29, 2020

Chiral sulfinyl compounds, sulfoxides, sulfoximines, sulfinamides, and other derivatives, play an important role in asymmetric synthesis as versatile auxiliaries, ligands, catalysts. They are also recognized pharmacophores found already marketed well-sold drugs (e.g., esomeprazole) used drug design. This review is devoted to the modern methods of preparation derivatives enantiopure or enantiomerically enriched form. Selected new approaches leading racemic products for which variant can be developed future mentioned well.

Language: Английский

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Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(41), P. 14653 - 14659

Published: Aug. 17, 2019

Abstract A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example intramolecular cyclization/cross‐coupling olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to number chiral compounds, such as dihydrobenzofurans, indolines, chromanes, indanes bearing quaternary stereocenter, in good yields excellent enantioselectivities. The practicality this validated modification biologically complex molecules peptides, piperitol, CB2 receptor agonists, etc. Moreover, synthesis two enantiomers can be easily realized simple change order steps sequence.

Language: Английский

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P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P–C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(51), P. 20556 - 20564

Published: Dec. 2, 2019

The development of transition-metal-catalyzed methods for the synthesis P-chiral phosphine derivatives poses a considerable challenge. Herein, we present direct Pd/Xiao-Phos-catalyzed cross-coupling reaction easily accessible secondary oxides and aryl bromides, which provides rapid access to oxides. proceeds efficiently with wide array partners deliver various tertiary in up 96% yield 97% ee. Moreover, DiPAMP ligand its analogues was also realized, demonstrates suitable pathway switching branched chain DiPAMP.

Language: Английский

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Palladium/XuPhos-Catalyzed Enantioselective Carboiodination of Olefin-Tethered Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(20), P. 8110 - 8115

Published: May 9, 2019

A highly enantioselective palladium-catalyzed iodine atom transfer cycloisomerization of unactivated alkenes has been developed. This represents the first example carboiodination olefin-tethered aryl iodides, which provides a perfect economy method to construct series optically active 2,3-dihydrobenzofuran, indolines and chromane bearing an alkyl iodide group in moderate good yields. Moreover, use readily available starting materials, broad substrate scope, high selectivity, mild reaction conditions, as well versatile transformation product make this approach attractive. The mechanism Pd(0)-catalyzed asymmetric investigated with density functional theory.

Language: Английский

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Enantioselective sulfinylation of alcohols and amines by condensation with sulfinates

Chem, Journal Year: 2024, Volume and Issue: 10(5), P. 1541 - 1552

Published: March 15, 2024

Language: Английский

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Enantioselective construction of stereogenic-at-sulfur(IV) centres via catalytic acyl transfer sulfinylation

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1301 - 1311

Published: May 8, 2024

Language: Английский

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Palladium‐Catalyzed Enantioselective Reductive Heck Reactions: Convenient Access to 3,3‐Disubstituted 2,3‐Dihydrobenzofuran

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(32), P. 10373 - 10377

Published: June 20, 2018

The first example of highly enantioselective intramolecular hydroarylation allyl aryl ethers was realized by palladium-catalyzed reductive heck reactions utilizing a new chiral sulfinamide phosphine ligand (N-Me-XuPhos). N-Me-XuPhos can be easily prepared on gram scale from readily available starting materials in one-pot synthesis approach. A series optically active 2,3-dihydrobenzofurans bearing quaternary stereocenter were obtained good yields and with excellent enantioselectivities. practicality this reaction validated the straightforward CB2 receptor agonists. Moreover, deuterium efficiently incorporated into products.

Language: Английский

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Enantioselective Difunctionalization of Alkenes by a Palladium‐Catalyzed Heck/Sonogashira Sequence

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(7), P. 2769 - 2775

Published: Nov. 22, 2019

Abstract Sonogashira‐type cross‐couplings are one of the most significant alkynylations in organic chemistry. One first palladium‐catalyzed intramolecular Heck/Sonogashira reactions alkenes with terminal alkynes is now reported. With this method, a variety uniquely substituted chiral benzene‐fused heterocycles bearing propargyl‐substituted all‐carbon quaternary stereocenter were obtained straightforward, high‐yielding, and highly stereoselective manner under mild conditions. Salient features process include use readily available substrates, high selectivities, broad substrate scope as well versatile product functionalizations.

Language: Английский

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Pd/PC‐Phos‐Catalyzed Enantioselective Intermolecular Denitrogenative Cyclization of Benzotriazoles with Allenes and N‐Allenamides

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(33), P. 11444 - 11448

Published: June 14, 2019

Abstract Reported herein is an asymmetric Pd/PC‐Phos‐catalyzed denitrogenative cyclization of benzotriazoles with allenes and N‐allenamides, representing the first example enantioselective cyclizations benzotriazoles. A series optically active 3‐methyleneindolines were obtained in good yields high ee values. The use inexpensive readily available starting materials, regio‐ enantioselectivity, a broad substrate scope, mild reaction conditions, no need for base, as well versatile functionalization make this approach attractive.

Language: Английский

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