Earth Abundant Transition Metal Catalysts: New and Efficient Tools for Hydrophosphination and Oxyphosphination of Alkenes and Alkynes DOI Creative Commons

Yumeng Yuan,

Christophe Darcel

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

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions DOI
Kuhali Das, Satyadeep Waiba, Akash Jana

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(11), С. 4386 - 4464

Опубликована: Янв. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Язык: Английский

Процитировано

163
Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins DOI Creative Commons

Danqing Ji,

Jierui Jing,

Yi Wang

и другие.

Chem, Год журнала: 2022, Номер 8(12), С. 3346 - 3362

Опубликована: Сен. 23, 2022

Язык: Английский

Процитировано

79
Asymmetric Hydrophosphinylation of Alkynes: Facile Access to Axially Chiral Styrene‐Phosphines DOI
Baohua Cai, Yuan Cui, Jian Zhou

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 25, 2022

Abstract A Cu/CPA co‐catalytic system has been developed for achieving the direct hydrophosphinylation of alkynes with phosphine oxides in delivering novel axially chiral phosphorus‐containing alkenes high yields and excellent enantioselectivities (up to 99 % yield ee). DFT calculations were performed elucidate reaction pathway origin enantiocontrol. This streamlined modular methodology establishes a new platform design application styrene‐phosphine ligands.

Язык: Английский

Процитировано

49
Metal‐Catalyzed Hydrophosphination DOI Creative Commons

Bryan T. Novas,

Rory Waterman

ChemCatChem, Год журнала: 2022, Номер 14(22)

Опубликована: Сен. 22, 2022

Abstract Organophosphines have garnered attention from many avenues ranging agriculture to fine chemicals. One‐time use of phosphate resources has made sustainable phosphorus overall imperative. Hydrophosphination serves as an efficient method selectively prepare P−C bonds, furnishing a range phosphorus‐containing molecules while maximizing the phosphorus. Since first report in 1958, wide array catalysts appeared for hydrophosphination, reaction that is spontaneous some instances. This review presents representative view literature based on known through mid‐2022, highlighting extensions unique substrates and advances selectivity. While several excellent reviews aspects this transformation, meant comprehensive guide reported catalysts.

Язык: Английский

Процитировано

48
Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes DOI Creative Commons
Jian Zhou, Ling Meng, Shujuan Lin

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 26, 2023

Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation regioselectivity and complicated reaction patterns. Herein, we report straightforward Pd-catalyzed ring-opening hydrophosphinylation MCPs via highly selective C-C bond cleavage. This method allows for rapid efficient access wide range chiral allylic phosphine oxides in good yields high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed elucidate mechanism origin enantioselectivity.

Язык: Английский

Процитировано

33
Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis DOI

Feixiang Sun,

Jiamin Huang,

Zhihong Wei

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 21, 2023

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis γ-disubstituted and β-disubstituted ketones is reported. Employing well-defined Mn-MACHOPh as catalyst, this novel protocol has a broad substrate scope with good functional group tolerance affords diverse library valuable disubstituted in moderate to yields. The strong influence reaction temperature on selective formation alcohol products was theorized preliminary DFT studies. Studies have shown that Gibbs free energy thermodynamically more favourable than corresponding at lower temperature.

Язык: Английский

Процитировано

31
Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines DOI Creative Commons
Qingjing Yang, Jian Zhou, Jun Wang

и другие.

Chemical Science, Год журнала: 2023, Номер 14(16), С. 4413 - 4417

Опубликована: Янв. 1, 2023

An enantioselective hydrophosphination of alkenyl isoquinolines is developed by using a copper-chiral diphosphine ligand catalyst. It provides direct and atom-efficient approach to prepare variety chiral phosphines with an isoquinoline unit in good yields high enantioselectivities. In addition, these phosphine products are useful bidentate P,N-ligands which showed potential application asymmetric catalysis.

Язык: Английский

Процитировано

27
Copper(I)‐Catalyzed Asymmetric Hydrophosphination of 3,3‐Disubstituted Cyclopropenes DOI
Shuai Zhang, Jiang Nan,

Jun‐Zhao Xiao

и другие.

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

27
Copper‐Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes** DOI

Brian S. Daniels,

Xintong Hou,

Stephanie A. Corio

и другие.

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
Unlocking the potential of metal ligand cooperation for enantioselective transformations DOI Creative Commons
Tizian‐Frank Ramspoth, Johanan Kootstra, Syuzanna R. Harutyunyan

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(7), С. 3216 - 3223

Опубликована: Янв. 1, 2024

Metal–ligand cooperation, (MLC) is a versatile catalysis concept. Herein, we discuss the historical context, mechanisms, and applications, suggesting exploring MLC for enantioselective transformations beyond (de)hydrogenative processes.

Язык: Английский

Процитировано

11