Shining Light on the Light-Bearing Element: A Brief Review of Photomediated C–H Phosphorylation Reactions

Synthesis, Journal Year: 2020, Volume and Issue: 53(06), P. 1003 - 1022

Published: Nov. 23, 2020

Abstract Organophosphorus compounds have numerous useful applications, from versatile ligands and nucleophiles in the case of trivalent organophosphorus species to therapeutics, agrochemicals material additives for pentavalent species. Although phosphorus chemistry is a fairly mature field, construction C–P(V) bonds relies heavily on either prefunctionalized substrates such as alkyl or aryl halides, requires previously oxidized C=N C=O, leading potential sustainability issues when looking at overall synthetic route. In light recent advances photochemistry, using photons reagent can provide better alternatives phosphorylations by unlocking radical mechanisms providing interesting redox pathways. This review will showcase different photomediated phosphorylation procedures available converting C–H into bonds. 1 Introduction 1.1 Compounds 1.2 Phosphorylation: Construction Bonds 1.3 Photochemistry an Alternative Classical Phosphorylations 2 Ionic Mechanisms Involving Nucleophilic Additions 3 Radical Intermediates 3.1 Reactive Carbon Radicals 3.2 Phosphorus 3.2.1 Photoredox: Direct Creation 3.2.2 Indirect 3.2.3 Dual Catalysis 3.3 Photolytic Cleavage 4 Conclusion Outlook

Language: Английский

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A catalytic enantioselective stereodivergent aldol reaction

Science Advances, Journal Year: 2023, Volume and Issue: 9(11)

Published: March 15, 2023

The aldol reaction is among the most powerful and strategically important carbon-carbon bond-forming transformations in organic chemistry. importance of constructing chiral building blocks for complex small-molecule synthesis has spurred continuous efforts toward development direct catalytic variants. realization a general with control over both relative absolute configurations newly formed stereogenic centers been longstanding goal field. Here, we report decarboxylative that provides access to all four possible stereoisomers product one step from identical reactants. mild can be carried out on large scale an open flask, generates CO2 as only by-product. method tolerates broad substrate scope β-hydroxy thioester products substantial downstream utility.

Language: Английский

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Phosphorylation of arenes, heteroarenes, alkenes, carbonyls and imines by dehydrogenative cross-coupling of P(O)–H and P(R)–H

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 20(3), P. 498 - 537

Published: Nov. 23, 2021

Organophosphorous compounds have recently emerged as a powerful class of with widespread applications, such in bioactive natural products, pharmaceuticals, agrochemicals and organic materials, ligands catalysis. The preparation these requires synthetic techniques novel catalytic systems varying from transition metal, photo- electrochemical catalysis to transformations without metal catalysts. Over the past few decades, addition P-H bonds alkenes, alkynes, arenes, heteroarenes other unsaturated substrates hydrophosphination related reactions via above-mentioned processes has an atom economical approach obtain organophosphorus compounds. In most cycles, bond is cleaved yield phosphorus-based radical, which adds onto substrate followed by reduction corresponding radical yielding product.

Language: Английский

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Triflylpyridinium Enables Rapid and Scalable Controlled Reduction of Carboxylic Acids to Aldehydes using Pinacolborane

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 15, 2022

Building up new and efficient methods for the controlled conversion of carboxylic acids to aldehydes is important. Herein, we report a rapid, modular scalable method using pinacolborane at ambient temperature, in which triflylpyridinium reagent used. The acid intermediate acylpyridinium by new. A binary pyridine-coordinated boronium complex generated after reduction. unprecedented reduction HBpin opens practically direct synthesis from acids. Theoretical studies indicate that requires lower activation free energy than product aldehyde. synthetic advantage this protocol further highlighted aldehyde via continuous flow process. Configuration retention chiral are presented those syntheses.

Language: Английский

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Visible-light-facilitated P-center radical addition to CX (X = C, N) bonds results in cyclizations

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(65), P. 7997 - 8002

Published: Jan. 1, 2021

Different strategies and new P-radical precursor induced C–P bond formation by visible light photocatalysis were summarized.

Language: Английский

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Different Lewis Acid Promotor-Steered Highly Regioselective Phosphorylation of Tertiary Enamides

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 9769 - 9781

Published: July 22, 2022

Different Lewis acid promotor-steered highly regioselective phosphorylation of tertiary enamides with diverse H-phosphonates or H-phosphine oxides was developed. Under the catalysis iron salt, phosphonyl group introduced into α-position enamides, affording various α-phosphorylated amides in high efficiency. On other hand, β-phosphorylated were efficiently obtained as products presence manganese(III) acetylacetonate.

Language: Английский

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Highly Enantio‐ and Diastereoselective Hydrogenation of Cyclic Tetra‐Substituted β‐Enamido Phosphorus Derivatives

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 11, 2023

Catalytic asymmetric hydrogenation of enamido phosphorus derivatives is one the most efficient methods for construction chiral amino products, among which congested tetra-substituted substrates remains an unaddressed challenge. In this study, we utilize a commercially available Rh-Josiphos system and stereoselective wide set cyclic β-enamido phosphonates/phosphine oxides, thus enabling access to β-amino compounds featuring two vicinal stereocenters. This protocol was broadly applicable different ring systems possessing various phosphonate/phosphine oxide groups further applied in preparation amino-phosphine ligands. DFT mechanistic explorations indicate that C=C migratory insertion into RhIII -H bond could be rate- stereo-determining step. The origins stereoselectivity are revealed through distortion/interaction analysis, primarily regulated by distinguished dispersion interactions steric repulsions.

Language: Английский

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Enantio- and Z -selective synthesis of functionalized alkenes bearing tertiary allylic stereogenic center

Science Advances, Journal Year: 2023, Volume and Issue: 9(2)

Published: Jan. 13, 2023

Olefins are ubiquitous in biologically active molecules and frequently used as building blocks chemical transformations. However, although many strategies exist for the synthesis of stereodefined E -olefines, their thermodynamically less stable Z counterparts substantially more demanding, while access to those bearing an allylic stereocenter with adjacent reactive functionality remains unsolved altogether. Even classic Wittig reaction, arguably most versatile widely approach construct -alkenes, falls short these particularly challenging yet highly useful structural motives. Here, we report a general methodology -selective functionalized chiral alkenes that establishes readily available alkene-derived phosphines alternative alkylating reagents olefination, thus offering previously unidentified retrosynthetic disconnections formation disubstituted alkenes. We demonstrate potential this method by diversification several bioactive molecules.

Language: Английский

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Phosphine Oxides (−POMe₂) for Medicinal Chemistry: Synthesis, Properties, and Applications

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(18), P. 12783 - 12801

Published: Sept. 1, 2021

A general practical approach to hetero(aromatic) and aliphatic P(O)Me2-substituted derivatives is elaborated. The key synthetic step was a [Pd]-mediated C-P coupling of (hetero)aryl bromides/iodides with HP(O)Me2. P(O)Me2 substituent shown dramatically increase solubility decrease lipophilicity organic compounds. This tactic used improve the antihypertensive drug prazosin without affecting its biological profile.

Language: Английский

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Ni-catalyzed regiodivergent hydrophosphorylation of enynes

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 34(6), P. 107914 - 107914

Published: Oct. 22, 2022

Language: Английский

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