Hydrosilylation of Aldehydes and Ketones Catalyzed by a 2-Iminopyrrolyl Alkyl-Manganese(II) Complex DOI
Tiago F. C. Cruz, Luı́s F. Veiros, Pedro T. Gomes

и другие.

Inorganic Chemistry, Год журнала: 2021, Номер 61(2), С. 1195 - 1206

Опубликована: Дек. 28, 2021

A well-defined and very active single-component manganese(II) catalyst system for the hydrosilylation of aldehydes ketones is presented. First, reaction 5-(2,4,6-iPr3C6H2)-2-[N-(2,6-iPr2C6H3)formimino]pyrrolyl potassium (KL) [MnCl2(Py)2] afforded binuclear 2-iminopyrrolyl pyridine chloride complex [Mn2{κ2N,N'-5-(2,4,6-iPr3C6H2)-NC4H2-2-C(H)═N(2,6-iPr2C6H3)}2(Py)2(μ-Cl)2] 1. Subsequently, alkylation 1 with LiCH2SiMe3 respective (trimethylsilyl)methyl-Mn(II) [Mn{κ2N,N'-5-(2,4,6-iPr3C6H2)-NC4H2-2-C(H)═N(2,6-iPr2C6H3)}(Py)CH2SiMe3] 2 in a good yield. Complexes were characterized by elemental analysis, 1H NMR spectroscopy, Evans' method, FTIR single-crystal X-ray diffraction. While crystal structure has been identified as entity, which Mn(II) centers present pentacoordinate coordination spheres, that corresponds to monomer distorted tetrahedral geometry. Complex proved be precatalyst atom-economic several under mild conditions, maximum turnover frequency 95 min-1, via silyl-Mn(II) mechanistic route, asserted combination experimental theoretical efforts, silanes cleanly converted alcoholic products high yields.

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
Manganese Catalyzed Acceptorless Dehydrogenative Coupling Reactions DOI
Satyadeep Waiba, Biplab Maji

ChemCatChem, Год журнала: 2019, Номер 12(7), С. 1891 - 1902

Опубликована: Дек. 21, 2019

Abstract Acceptorless dehydrogenative coupling (ADC) has emerged as a powerful tool in the chemists’ arsenal for construction of various carbon‐carbon and carbon‐heteroatom bonds. These protocols are highly atom economical environmentally benign they do not require pre‐functionalized starting material produce only dihydrogen (and water) by‐product. This technique, coupled with Earths’ abundant less toxic manganese catalysis, can prove to be vital strategy generation molecular complexity from simple materials. Manganese catalyzed DHC been growing interest, low‐ high‐valent catalysts have developed. were demonstrated show excellent catalytic activity formation carbon‐carbon, bonds, cascade reactions. In this mini‐review, we would like highlight recent progress that made ADC

Язык: Английский

Процитировано

95
Highly Selective Synthesis of 1,3-Enynes, Pyrroles, and Furans by Manganese(I)-Catalyzed C–H Activation DOI
Sara Cembellín, Toryn Dalton,

Tobias Pinkert

и другие.

ACS Catalysis, Год журнала: 2019, Номер 10(1), С. 197 - 202

Опубликована: Ноя. 21, 2019

A highly selective Mn(I)-catalyzed alkenylation of arenes and heteroarenes with 1,3-diynes is described. The reported transformation overcomes regio-, chemo-, stereoselectivity challenges associated the use these coupling partners. Both symmetrical unsymmetrical diynes can be applied in this protocol, affording single isomers not only synthesis 1,3-enynes but also one-step preparation pyrroles furans. This simple strategy features wide functional group tolerance, good reproducibility, preparative scale utility. manganese catalyst plays a crucial role C–H activation enabling high selectivity previously challenging internal alkynes. Furthermore, synthetic value method highlighted by diverse postsynthesis functionalizations final products.

Язык: Английский

Процитировано

92
Phosphine-Free Manganese Catalyst Enables Selective Transfer Hydrogenation of Nitriles to Primary and Secondary Amines Using Ammonia–Borane DOI
Koushik Sarkar, Kuhali Das, Abhishek Kundu

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(5), С. 2786 - 2794

Опубликована: Фев. 15, 2021

Herein we report the synthesis of primary and secondary amines by nitrile hydrogenation, employing a borrowing hydrogenation strategy. A class phosphine-free manganese(I) complexes bearing sulfur side arms catalyzed reaction under mild conditions, where ammonia–borane is used as source hydrogen. The synthetic protocol chemodivergent, final product either or amine, which can be controlled changing catalyst structure polarity medium. significant advantage this method that operates without externally added base other additives well obviates use high-pressure dihydrogen gas required for reactions. Utilizing method, wide variety symmetric asymmetric were synthesized in high yields. mechanistic study involving kinetic experiments high-level DFT computations revealed both outer-sphere dehydrogenation inner-sphere predominantly operative catalytic cycle.

Язык: Английский

Процитировано

68
Advancements in multifunctional manganese complexes for catalytic hydrogen transfer reactions DOI
Kuhali Das, Milan Kr. Barman, Biplab Maji

и другие.

Chemical Communications, Год журнала: 2021, Номер 57(69), С. 8534 - 8549

Опубликована: Янв. 1, 2021

Manganese catalyzed hydrogen transfer reactions enabled net reductions and cascade CC- CN-bond formation reactions. The success is aided by multifunctional ligand design namely metal–ligand bifunctionality, hemilability, redox non-innocence.

Язык: Английский

Процитировано

61
Unleashing the potentiality of metals: synergistic catalysis with light and electricity DOI
Zhengjia Shen, Jia‐Lin Tu, Binbin Huang

и другие.

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4024 - 4040

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Язык: Английский

Процитировано

13
Recent advances in the diversification of chromones and flavones by direct C H bond activation or functionalization DOI

Shanghui Tian,

Tian Luo,

Yanping Zhu

и другие.

Chinese Chemical Letters, Год журнала: 2020, Номер 31(12), С. 3073 - 3082

Опубликована: Июль 26, 2020

Язык: Английский

Процитировано

58
Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis DOI
Kuhali Das, Koushik Sarkar, Biplab Maji

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(12), С. 7060 - 7069

Опубликована: Июнь 2, 2021

Controlling the selectivity in a hydroamination reaction is an extremely challenging yet highly desirable task for diversification of amines. In this article, selective formal anti-Markovnikov allyl alcohols presented. It enables versatile synthesis valuable γ-amino alcohol building blocks. A phosphine-free Earth's abundant manganese(I) complex catalyzed under hydrogen-borrowing conditions. vast range aliphatic, aromatic amines, drug molecules, and natural product derivatives underwent successful with primary secondary allylic excellent functional group tolerance (57 examples). The catalysis could be performed on gram scale has been applied molecules. mechanistic studies revealed metal–ligand bifunctionality as well hemilability ligand backbone key design principle success catalysis.

Язык: Английский

Процитировано

48
Manganese-Catalyzed Carbonylation of Unactivated Alkyl Bromides with Alkylidenecyclopropanes DOI

Peng-Rui Liu,

Miao-Miao Ji,

Jian-Bang Hu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9487 - 9495

Опубликована: Июнь 7, 2024

Язык: Английский

Процитировано

8
Cobalt(III)-Catalyzed Regioselective C6 Olefination of 2-Pyridones Using Alkynes: Olefination/Directing Group Migration and Olefination DOI
Xin Xu, Lin Zhang, Haoqiang Zhao

и другие.

Organic Letters, Год журнала: 2021, Номер 23(12), С. 4624 - 4629

Опубликована: Июнь 9, 2021

Co(III)-catalyzed highly regio- and stereoselective direct C6 olefination of 2-pyridones with alkynes has been developed the assistance chelation. Upon variation reaction conditions, react well diaryl via a olefination/directing group migration pathway to give tetrasubstituted 6-vinyl-2-pyridones, but C6-H terminal works effectively afford only C6-olefinated 2-pyridones. A judicious choice solvent an additive is crucial for catalysis. The protocols feature 100% atom economy, excellent site selectivity, high stereoselectivity, ample substrate scope, good compatibility functional groups. Synthetic applications are demonstrated, experimental studies density theory calculations conducted gain mechanistic insight into two transformations.

Язык: Английский

Процитировано

36