Chemical Science, Год журнала: 2024, Номер 15(30), С. 12006 - 12016
Опубликована: Янв. 1, 2024
The acid-mediated cyclisation of sterically encumbered cyclic triphosphanes with nitriles provides access to five-membered cationic and neutral P 3 CN heterocycles tuneable colour.
Язык: Английский
ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6994 - 7001
Опубликована: Май 9, 2023
A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio- enantioselectivity easily derivatized to structurally diverse chiral compounds. Mechanistic studies on both Ni0-catalyzed Markovnikov addition NiII-catalyzed have been carried out combining experimental computational methods. In the Ni0 system, an allyl nickel complex as catalyst resting state whose structure unambiguously determined single-crystal XRD analysis. sequential hydrometallation, ligand exchange, reductive elimination mechanism elucidated corroboratively DFT calculations. cationic secondary serves active catalyst. migratory insertion protonation sequence operative accomplish hydrophosphination.
Язык: Английский
Процитировано
26
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)
Опубликована: Июнь 19, 2023
We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. Enrichment phosphorus stereocenters is also demonstrated via Dynamic Kinetic Asymmetric Transformation (DyKAT) process. combined experimental theoretical mechanistic study supports an elementary step featuring insertion Cu
Язык: Английский
Процитировано
25
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)
Опубликована: Авг. 18, 2023
Herein, a copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported. It provides series phosphine derivatives in high to excellent diastereo- and enantioselectivities. The methodology enjoys broad substrate scope on both diarylphosphines. stereoselectivity attributed the stability Cu(I)-(R,R)-QUINOXP* complex presence stoichiometric HPPh2 produced phosphines, high-performance induction complex. Finally, method used for synthesis new chiral phosphine-olefin compounds built cyclopropane skeleton, one which serves as wonderful ligand Rh-catalyzed conjugate addition phenylboronic acid various α,β-unsaturated compounds.
Язык: Английский
Процитировано
25
Molecules, Год журнала: 2024, Номер 29(3), С. 688 - 688
Опубликована: Фев. 1, 2024
Rare earths, scandium, yttrium, and the fifteen lanthanoids from lanthanum to lutetium, are classified as critical metals because of their ubiquity in daily life. They present magnets cars, especially electric cars; green electricity generating systems computers; steel manufacturing; glass light emission materials for safety lighting lasers; exhaust catalysts supports; artificial rubber production; agriculture animal husbandry; health cancer diagnosis treatment; a variety electronic products essential modern living. have potential replace toxic chromates corrosion inhibition, magnetic refrigeration, new materials, role may expand. This review examines sustainability, environment, recycling, crop production, feedstocks, catalysis, health, well considering future uses.
Язык: Английский
Процитировано
10
Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
This review highlights recent advances in the hydrofunctionalisation of cyclopropenes through formation carbon–heteroatom bonds for synthesis polysubstituted cyclopropanes.
Язык: Английский
Процитировано
1
Chemical Communications, Год журнала: 2023, Номер 59(10), С. 1258 - 1273
Опубликована: Янв. 1, 2023
An examination of several catalytic reactions among the group 15 elements is presented. The connections between chemistry pnictogens can sometimes be challenging, but aspects metal-pnictogen reactivity are key. connecting comes from metal-catalyzed transformations such as dehydrocoupling and hydrofunctionalization. Pivotal mechanistic insights E-N heterodehydrocoupling have informed development highly active catalysts for these reactions. Metal-amido nucleophilicity often at core this reactivity, which diverges phosphine arsine dehydrocoupling. Nucleophilicity connects to earliest understanding hydrophosphination catalysis, more recent leveraging enhanced insertion activity through photolysis. This photocatalysis extends hydroarsination, may also metal-arsenido than anticipated. However, arsinidene foreshadowed related phosphinidene by years. shows potential greater influence individual discoveries leverage new advances elements, it suggests that heavier on what possible with lighter elements.
Язык: Английский
Процитировано
12
Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown
Опубликована: Окт. 5, 2024
P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio- enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.
Язык: Английский
Процитировано
4
Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)
Опубликована: Дек. 22, 2023
Abstract This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful diverse range alkenyl‐heteroarenes with high enantioselectivity. presented protocol addresses inherently low reactivity and commonly encountered suboptimal enantioselectivities these challenging substrates. As an important application we show that this method facilitates synthesis non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using single catalytic system.
Язык: Английский
Процитировано
9
ChemCatChem, Год журнала: 2024, Номер unknown
Опубликована: Май 27, 2024
Abstract Hydrophosphination and oxyphosphination are two important topical reactions in order to prepare organophosphorus derivatives from unsaturated such as alkenes alkynes a more sustainable fashion. Noticeably, metal catalysed versions have shown great interest efficiency. By contrast, the use of earth abundant transition based catalysts for transformations is less reported, even if there growing during last decade. This review article reports highlights recent developments using manganese, iron, cobalt, nickel copper hydro‐ oxyphosphination, notably exhibiting selectivity, functional group tolerance, milder conditions catalyst design. Even significant progresses were made, scopes still rather limited (mainly focused on activated olefins styrenes) chemo‐ stereo‐selectivity issues be solved, asymmetric transformations. Of interest, visible light including blue one activator emerged, giving promising stimulating results at ambient conditions.
Язык: Английский
Процитировано
3
Green Synthesis and Catalysis, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Процитировано
0