Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Language: Английский

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Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(42), P. 13735 - 13747

Published: June 6, 2018

Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening decarboxylative catalytic transformations allowing the development of new stereo- enantioselective C-N, C-O, C-C, C-S C-B bond formation reactions. Transition-metal-mediated conversions only recently been rejuvenated powerful approaches towards preparation more complex molecules. This minireview will highlight potential structurally with a focus on their synthetic value mechanistic manifolds that are involved upon conversion.

Language: Английский

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Highly Enantioselective [5 + 2] Annulations through Cooperative N-Heterocyclic Carbene (NHC) Organocatalysis and Palladium Catalysis

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(10), P. 3551 - 3554

Published: Feb. 22, 2018

The highly enantioselective [5 + 2] annulation of enals with vinylethylene carbonates through a cooperative N-heterocyclic carbene (NHC)/Pd catalytic system is reported. use bidentate phosphine ligand was crucial to prevent coordination the NHC organocatalyst active Pd catalyst. complementary and matched combination chiral catalyst promotes high levels both reactivity enantioselectivity (mostly ≥99% ee).

Language: Английский

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Enantioselective Trapping of Pd-Containing 1,5-Dipoles by Photogenerated Ketenes: Access to 7-Membered Lactones Bearing Chiral Quaternary Stereocenters

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 141(1), P. 133 - 137

Published: Dec. 12, 2018

An enantioselective [5+2] cycloaddition of vinylethylene carbonates and α-diazoketones was achieved for the first time by merging photoactivation asymmetric Pd catalysis. The key to success this method is trapping Pd-containing, 1,5-dipolar intermediates ketenes, a class reactive C2 synthons, which were generated in an situ traceless manner under visible light irradiation. Through trapping, variety 7-membered lactones bearing challenging chiral quaternary stereocenters can be accessed facile with good efficiency high enantioselectivity (up 99% yield 96:4 er).

Language: Английский

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Pd‐Catalyzed Enantioselective [6+4] Cycloaddition of Vinyl Oxetanes with Azadienes to Access Ten‐Membered Heterocycles

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(6), P. 1596 - 1600

Published: Dec. 19, 2017

Abstract We report herein the first enantioselective cycloaddition of vinyl oxetanes, reaction which with azadienes provided unprecedented access to ten‐membered heterocycles through a [6+4] cycloaddition. By using commercially available chiral Pd‐SIPHOX catalyst, wide range benzofuran‐ as well indole‐fused could be accessed in excellent yield and enantioselectivity. A unique Lewis acid induced fragmentation these was also discovered.

Language: Английский

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Enantio‐ and Diastereodivergent Synthesis of Spirocycles through Dual‐Metal‐Catalyzed [3+2] Annulation of 2‐Vinyloxiranes with Nucleophilic Dipoles

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(47), P. 24941 - 24949

Published: Sept. 17, 2021

The development of efficient and straightforward methods for obtaining all optically active isomers structurally rigid spirocycles from readily available starting materials is great value in drug discovery chiral ligand development. However, the stereodivergent synthesis bearing multiple stereocenters remains an unsolved challenge owing to steric hindrance ring strain. Herein, we report enantio- diastereodivergent through dual-metal-catalyzed [3+2] annulation oxy π-allyl metallic dipoles with less commonly employed nucleophilic (imino esters). A series spiro compounds a pyrroline olefin were easily synthesized manner (up 19:1 dr, >99 % ee), which showed promise as new type N-olefin ligand. Preliminary mechanistic studies also carried out understand process this bimetallic catalysis.

Language: Английский

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High-order dipolar annulations with metal-containing reactive dipoles

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(10), P. 4146 - 4174

Published: Jan. 1, 2022

The advances on metal-catalysed high-order dipolar annulations were comprehensively summarized in this review. To further exploit the potential of unique annulation strategy, a research outlook was also proposed.

Language: Английский

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Atroposelective Synthesis of 1,1′‐Bipyrroles Bearing a Chiral N−N Axis: Chiral Phosphoric Acid Catalysis with Lewis Acid Induced Enantiodivergence

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(16)

Published: Feb. 17, 2022

Abstract We present herein a highly efficient atroposelective synthesis of axially chiral 1,1′‐bipyrroles bearing an N−N linkage from simple hydrazine and 1,4‐diones. Further product derivatizations led to bifunctional compounds with high potential in asymmetric catalysis. For this chrial phosphoric acid (CPA)‐catalyzed double Paal–Knorr reaction, intriguing Fe(OTf) 3 ‐induced enantiodivergence was also observed.

Language: Английский

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Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(9)

Published: Jan. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Language: Английский

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Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with β-Nitroolefins by Cooperative Catalysis of Palladium Complex and Squaramide

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(12), P. 11600 - 11604

Published: Nov. 2, 2018

An efficient method for the enantio- and diastereoselective construction of multisubstituted tetrahydrofurans via asymmetric decarboxylative cycloaddition vinylethylene carbonates with β-nitroolefins under a cooperative catalysis palladium complex squaramide is developed. By using generated in situ from Pd2(dba)3·CHCl3 phosphoramidite L1 chiral OC4 as catalysts mild conditions, process provided bearing quaternary stereocenter good to high yields acceptably diastereoselectivities.

Language: Английский

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