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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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

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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Synthesis of a Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis

Chem, Journal Year: 2020, Volume and Issue: 6(4), P. 994 - 1006

Published: March 9, 2020

Rotaxanes are interlocked molecules in which a molecular ring is trapped on dumbbell-shaped axle because of its inability to escape over the bulky end groups, resulting so-called mechanical bond. Interlocked have mainly been studied as components machines, but crowded, flexible environment created by threading one molecule through another has also explored catalysis and sensing. However, so far, applications most intriguing properties molecules, their ability display stereogenic units that do not rely stereochemistry covalent subunits, termed "mechanical chirality," yet be properly explored, prototypical demonstration mechanically chiral rotaxanes remain scarce. Here, we describe planar rotaxane-based Au complex mediates cyclopropanation reaction with stereoselectivities comparable best conventional catalyst reported for this reaction.

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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Palladium/PC-Phos-Catalyzed Enantioselective Arylation of General Sulfenate Anions: Scope and Synthetic Applications

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(9), P. 3467 - 3473

Published: Feb. 8, 2018

Herein we reported an efficient palladium-catalyzed enantioselective arylation of both alkyl and aryl sulfenate anions to deliver various chiral sulfoxides in good yields (up 98%) with excellent enantioselectivities 99% ee) by the use our developed O,P-ligands (PC-Phos). PC-Phos are easily prepared short steps from inexpensive commercially available starting materials. The single-crystal structure PC4/PdCl2 showed that a rarely observed 11-membered ring was formed via O,P-coordination palladium(II) center. salient features this method include general substrate scope, ease scale-up, applicable late-stage modification bioactive compounds, synthesis marketed medicine Sulindac.

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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Pd-Catalyzed Enantioselective Heck Reaction of Aryl Triflates and Alkynes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(49), P. 19246 - 19251

Published: Nov. 20, 2019

The first palladium-catalyzed asymmetric Heck reaction between aryl triflates and alkynes to give trisubstituted allenes with high er under mild conditions is described. key the success discovery fine-tuning of different N-substituents Xu-Phos, which ensure enantioselectivity reactivity. Synthetic transformation chiral chirality transfer was also demonstrated.

Language: Английский

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