Progress in design and applications of supramolecular assembly of 2,2′:6′,2″-terpyridine-based first row d-block elements

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 506, P. 215619 - 215619

Published: Feb. 16, 2024

Language: Английский

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Insights into Recent Nickel-Catalyzed Reductive and Redox C–C Coupling of Electrophiles, C(sp³)–H Bonds and Alkenes

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(8), P. 1149 - 1162

Published: March 28, 2024

ConspectusTransition metal-catalyzed reductive cross-coupling of two carbon electrophiles, also known as cross-electrophile coupling (XEC), has transformed the landscape C–C chemistry. Nickel catalysts, in particular, have demonstrated exceptional performance facilitating XEC reactions, allowing for diverse elegant transformations by employing various electrophiles to forge bonds. Nevertheless, several crucial challenges remain be addressed. First, intrinsic chemoselectivity between structurally similar Ni-catalyzed C(sp3)–C(sp3) and C(sp2)–C(sp2) not been well understood; this necessitates an excess one partners achieve synthetically useful outcomes. Second, substitution economically environmentally benign nonmetal reductants Zn/Mn can help scale up reactions avoid trace metals pharmaceutical products, but research direction progressed slowly. Finally, it is highly warranted leverage mechanistic insights from develop innovative thermoredox protocols, specifically designed tackle associated with difficult substrates such C(sp3)–H bonds unactivated alkenes.In Account, we address aforementioned issues reviewing our recent work on C–X C–O strategy alkenes, use diboron esters coupling. We focus perspectives transformations, particularly how key C–NiIII–C intermediates are generated, order explain chemoselective regioselective results. The Account consists four sections. discuss Zn/Mn-mediated bond formations based selected alkyl/aryl, allyl/benzyl, other electrophiles. describe versatile C(sp3)–C(sp2) couplings, emphasis consideration construction Third, leveraging C(sp3)–O effective C(sp3)–C formation via situ halogenation alcohols preparation α-vinylated -arylated unusual amino esters. In final section, illustrate functionalization challenging aryl alkyl halides afford taking advantage compatibility Zn oxidant di-tert-butylperoxide (DTBP). Furthermore, a SiH/DTBP-mediated hydrodimerization terminal alkenes selectively head-to-head methyl branched This process, conducted presence or absence catalytic CuBr2, provides solution long-standing challenge: site-selective hydrocoupling produce

Language: Английский

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The impact of earth-abundant metals as a replacement for Pd in cross coupling reactions

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9016 - 9025

Published: Jan. 1, 2024

Initial calculations of environmental footprints associated with using Ni vs Pd catalysis in a representative metal-catalyzed Suzuki–Miyaura cross-coupling reveal that the choice ligated metal is often NOT consequence. Rather, it culmination other parameters such as medium.

Language: Английский

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Supply and demand of platinum group metals and strategies for sustainable management

Renewable and Sustainable Energy Reviews, Journal Year: 2024, Volume and Issue: 204, P. 114821 - 114821

Published: Aug. 10, 2024

Language: Английский

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Recent Advances in C(sp³)–C(sp³) Cross-Coupling Chemistry: A Dominant Performance of Nickel Catalysts

Organometallics, Journal Year: 2022, Volume and Issue: 41(6), P. 667 - 679

Published: March 4, 2022

The formation of a new C–C bond at sp3-hybridized centers is highly desirable, as it opens up unique, unexplored chemical space. revolutionary discoveries in this field meet the longstanding challenge forming stereocontrolled bonds and provide rapid access to C(sp3)-rich drug molecules. improved catalytic systems have enabled creative design challenging transformations. latest advancements nickel catalysis are particularly attractive shown excellent performance field. progress that has been made toward C(sp3)–C(sp3) (traditional cross-electrophile couplings) past decade highlighted review.

Language: Английский

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Machine Learning Yield Prediction from NiCOlit, a Small-Size Literature Data Set of Nickel Catalyzed C–O Couplings

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14722 - 14730

Published: Aug. 8, 2022

Synthetic yield prediction using machine learning is intensively studied. Previous work has focused on two categories of data sets: high-throughput experimentation data, as an ideal case study, and sets extracted from proprietary databases, which are known to have a strong reporting bias toward high yields. However, predicting yields published reaction remains elusive. To fill the gap, we built set nickel-catalyzed cross-couplings organic publications, including scope optimization information. We demonstrate importance source failed experiments emphasize how publication constraints shape exploration chemical space by synthetic community. While models still fail perform out-of-sample predictions, this shows that adding knowledge enables fair predictions in low-data regime. Eventually, hope unique public database will foster further improvements methods for more realistic context.

Language: Английский

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Accelerated Direct Hydroxylation of Aryl Chlorides with Water to Phenols via the Proximity Effect in a Heterogeneous Metallaphotocatalyst

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(10), P. 6068 - 6080

Published: May 6, 2022

The proximity of different active sites in multi-catalytic systems is crucial influencing the catalytic reactions, that is, to occur or be accelerated. Here, we reported a heterogeneous metallaphotocatalyst prepared by embedding Ni(II) species photosensitive covalent organic framework (COF). A concerted triad behavior executed electrons, holes, and Ni triggered dramatic enhancement activation aryl chlorides with water phenols. It demonstrated 50-fold increment its activity when compared homogeneous analogy, for example, Ni(BPDA)Br2. Also, it was able efficiently activate variety corresponding phenols moderate high yields. Interestingly, effective even base-sensitive substituents chlorobenzene bearing NH NH2 groups. On basis detailed experiments, photoactive COF facilitates rapid electron transfer produce Ni(I) oxidative addition. Meanwhile, photogenerated holes oxidized hydroxyl radical, which then attacked Ni(III) intermediates complete cycle.

Language: Английский

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Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(7), P. 1160 - 1184

Published: March 20, 2023

Earth-abundant metal (EAM) catalysis can have profound impact in the pharmaceutical industry terms of sustainability and cost improvements from replacing precious metals like palladium as well harnessing differential reactivity first-row that allows for novel transformations to enable more efficient routes clinical candidates. The strategy building these capabilities within process group at Bristol Myers Squibb is described herein, with general plan a reaction screening platform, demonstrating scalability, increasing mechanistic understanding catalyst activation. development catalytic utilizing nickel, cobalt, iron while highlighting importance collaboration internal external groups advance EAM our portfolio. challenges benefits working transition metals, including metrics implementation catalysis, such cost, mass intensity, commercial availability catalysts ligands, are discussed.

Language: Английский

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Insights into the bacterial synthesis of metal nanoparticles

Frontiers in Nanotechnology, Journal Year: 2023, Volume and Issue: 5

Published: Aug. 10, 2023

Metal nanoparticles have attracted considerable attention due to their astounding potential for a wide range of commercial applications. From targeted drug delivery and antimicrobial agents electronics, metal seem immeasurable prospects in all areas science. However, modern industrial production frequently involves complex procedures, large amounts energy, utilizes strong chemical solvents, or produces hazardous waste. Biological synthesis has been proposed as an alternative simpler, inexpensive, more eco-friendly nanoparticle production. Microorganisms possess multiple mechanisms transport, regulate bind ions that may result the biosynthesis nanoparticles. They can synthesize even bimetallic nanoparticles, which are difficult produce with normal physical processes. A better understanding bacteria-metal interactions might thus pave way array This review will summarize current methods synthesis, focus on microbial (bio) We describe general ion interactions, including cellular uptake subsequent reduction into Protocols metal-based relevant elements different bacterial strains compiled challenges industry discussed.

Language: Английский

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Selective C(aryl)–O bond cleavage in biorenewable phenolics

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(11), P. 5489 - 5551

Published: Jan. 1, 2024

Selective removal of the hydroxy, methoxy or both groups in biorenewable oxygenated arenes (derived from lignin depolymerization) provides, respectively, anisoles, phenols and benzenes.

Language: Английский

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