Iron-Catalyzed Transfer Hydroalumination of Alkynes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

The limited availability of efficient synthetic methods for organoaluminum compounds constrains their broader applications. transfer hydroalumination alkynes emerges as a promising strategy synthesizing alkenylaluminum species; however, achieving precise control the selectivity remains formidable challenge. Herein, we disclose highly chemo-, regio-, and stereoselective alkynes, catalyzed by well-defined iron complexes, utilizing commercially available AlEt3 reagent. regioselectivity reaction involving terminal can be effectively modulated changing 2,9-aryl substituents on ligands with observation cis-α-selectivity not previously documented in literature. Furthermore, demonstrate unprecedented cis-β-selective simple unsymmetrical internal alkynes. This work only broadens scope reactions but also enhances methodologies diversity compounds, highlighting significant potential catalysts development organometallic reagents.

Language: Английский

---

Electride-Induced Electron Transfer to Metal Phthalocyanines: A Mechanistic and Catalytic Study

Chemistry of Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 4, 2025

Language: Английский

---

Cobalt-Catalyzed Regio- and Stereoselective Hydrosilylation of Alk-2-ynes with Tertiary Silanes

Organometallics, Journal Year: 2023, Volume and Issue: 42(14), P. 1693 - 1698

Published: Jan. 9, 2023

Selectivity control in the addition reactions of internal alkynes that bear two similar substituents presents a big challenge modern organic synthesis. Herein we report β-(E)-selective hydrosilylation alk-2-ynes with tertiary silanes can be achieved by using Co2(CO)8 as catalyst. Under catalytic reaction conditions, wide range converted into vinylsilanes β-(E) isomers major or sole products. Mechanistic studies suggest alkyne-bridged dicobalt species are likely intermediates. Steric repulsion between alkenyl-bridged silyl intermediates is proposed key factor inducing observed regioselectivity.

Language: Английский

---

Perspective for Phosphine Ligands with Cyclopropane Backbone^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(7), P. 777 - 777

Published: Jan. 1, 2023

Throughout the history of transition-metal catalysis, almost every breakthrough is closely related to development ligands.Therefore, catalysis roughly parallels ligand lies in heart transition metal catalysis.Since beginning homogeneous metals have been accompanied by phosphine ligands (Wilkinson's catalyst).Till now, are one most widely used types.There several key factors for popularity ligands, among which backbone plays a decisive role supporting their stability, activity and selectivity.Many privileged contain five-or six-membered rings core structures, possibly due ready-availability, low ring strain, high stability.Seven-and above membered cyclic structures flexible frameworks, many stable conformations, difficult synthesize, making them unsuitable as backbones.The cyclobutane structure has relatively strong but its conformation can be flipped, it inappropriate skeleton, too.As smallest all-carbon ring, three carbon atoms cyclopropane located same plane.Because unique electronic rigidity cyclopropane, changing substituent on any will affect substituents other two carbons.And simple synthesize modify, promising skeleton.However, surprising that with rarely studied so far, applications need further explored, too.Based types this perspective systematically summarizes reported phosphine-containing (including monophosphines, diphosphines, phosphine-heteroatoms triphosphines) backbone, catalysis.We hope draw researchers' attention cyclopropane-based thus promote catalysis.

Language: Английский

---

Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871

Published: Jan. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Language: Английский

---

Nickel-Catalyzed Enantioselective Hydrophosphinylation of 2-Azadienes to Access Enantioenriched α-Aminophosphine Oxides

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 10887 - 10894

Published: Aug. 3, 2023

The practical synthesis of C-stereogenic α-aminophosphine oxides, which exhibit a wide range applications in medicinal chemistry, biochemistry, material science, and asymmetric catalysis, represents an unmet need. Herein, Ni/(S,S)-BenzP* catalyst system is developed for branched oxides through enantioselective Markovnikov addition H-phosphine to 2-azadienes. A variety readily available 2-azadienes undergo hydrophosphinylation with high enantioselectivities (up 99%) good yields 96%). These products can be hydrolyzed afford synthetically valuable chiral are key building blocks the bioactive compounds (such as phospholeucine synthesized herein), organocatalysts, ligands. Mechanistic studies suggest hydrofunctionalization process.

Language: Английский

---

Experimental and Computational Studies on Cobalt(I)‐Catalyzed Regioselective Allylic Alkylation Reactions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

Abstract Here, we report the development of cobalt(I)‐catalyzed regioselective allylic alkylation reactions tertiary allyl carbonates with 1,3‐dicarbonyl compounds. A family well‐defined tetrahedral cobalt(I) complexes bearing commercially available bidentate bis(phosphine) ligands [(P,P)Co(PPh 3 )Cl] are synthesized and explored as catalysts in reactions. The catalyst [(dppp)Co(PPh (dppp=1,3‐Bis(diphenylphosphino)propane) enables a large variety high yields excellent regioselectivity for branched product. Remarkably, this methodology is selective activation even presence secondary carbonates. This contrasts selectivity observed cobalt‐catalyzed alkylations enabled by visible light photocatalysis. Mechanistic insights means experimental computational investigations support Co(I)/Co(III) catalytic cycle.

Language: Английский

---

Regioselective Hydroboration of Unsymmetrical Internal Alkynes Catalyzed by a Cobalt Pincer-NHC Complex

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5862 - 5867

Published: June 27, 2024

Highly regioselective hydroboration of unsymmetrical internal alkynes remains a significant challenge for synthesizing valuable alkenylboronate esters. Herein, we describe an easily synthesizable pincer NHC-based Co complex as catalyst the cis-α selective unactivated and cis-β activated with pinacolborane. The reaction showcases high chemo-, regio-, stereoselectivity, displays efficiency very low loading under base-free conditions. scope was demonstrated by having variety functional groups. mechanistic studies suggest feasible Co-boryl intermediate to explain unusual regioselectivity.

Language: Английский

---

Copper‐Metallized Porous N‐Heterocyclic Carbene Ligand Polymer‐Catalyzed Regio‐ and Stereoselective 1,2‐Carboboration of Alkynes

Advanced Science, Journal Year: 2023, Volume and Issue: 11(7)

Published: Dec. 8, 2023

Alkenylboronates are highly versatile building blocks and valuable reagents in the synthesis of complex molecules. Compared with that monosubstituted alkenylboronates, multisubstituted alkenylboronates is challenging. The copper-catalyzed carboboration alkynes an operationally simple straightforward method for synthesizing bis/trisubstituted alkenylboronates. In this work, a series copper-metallized N-Heterocyclic Carbene (NHC) ligand porous polymer catalysts designed synthesized accordance mechanism carboboration. By using CuCl@POL-NHC-Ph as optimal nanocatalyst, study realizes β-regio- stereoselective (syn-addition) 1,2-carboboration (regioselectivity up to >99:1) satisfactory yields wide range substrates. This work not only overcomes selectivity but also provides new strategy design nanocatalysts their application organic synthesis.

Language: Английский

---

LiO^tBu-Promoted trans-Stereoselective and β-Regioselective Hydroboration of Propargyl Alcohols

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6401 - 6406

Published: Aug. 21, 2023

A convenient and efficient trans-stereoselective β-regioselective hydroboration of propargyl alcohols was achieved simply with LiOtBu as the base (Bpin)2 boron reagent in dimethyl sulfoxide at room temperature. Both terminal internal diverse structures functional groups underwent transformation smoothly to produce β-Bpin-substituted (E)-allylic alcohols, which synthetic potentials were demonstrated by downstream conversions boronate, alkenyl, hydroxyl groups.

Language: Английский

---