Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation DOI Creative Commons
Arnaud Clerc,

M. Humbert,

Sonia Mallet‐Ladeira

и другие.

ChemistryEurope, Год журнала: 2024, Номер 3(1)

Опубликована: Ноя. 12, 2024

Abstract With the aim to explore metal‐ligand cooperation across Pd−S linkages, we designed a quinoline‐based PNS tridentate ligand and prepared Pd(II) complexes thereof. Optimal solubility stability of dicationic complex [(PNS)Pd(II)] 2 2+ IV were achieved with B(C 6 F 5 ) 4 – as counter‐anion. It adopts thiolate‐bridged dimeric structure (PdS) core, but readily activates hydrosilanes linkage. The resulting mononuclear hydride [(PNS SiR3 )Pd(II)H] + VI was characterized by multi‐nuclear NMR spectroscopy Si−H bond coordination/activation studied computationally. Complex found efficiently catalyze hydrosilylation alkynes, internal well terminal, good stereo regioselectivity.

Язык: Английский

Broadly Applicable Copper(I)-Catalyzed Alkyne Semihydrogenation and Hydrogenation of α,β-Unsaturated Amides Enabled by Bifunctional Iminopyridine Ligands DOI Creative Commons

Mahadeb Gorai,

J. Franzen,

Philipp Rotering

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 16, 2025

A highly active bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene complex and basic 2-iminopyridine subunit allows for copper hydride chemistry under low H2 pressure, achieving efficient catalysis reaching 1 bar (balloon pressure). The tolerates remarkable variety functional groups in catalytic alkyne semihydrogenations. Furthermore, this design gives rise to high reactivity that the hydrogenation α,β-unsaturated amides (a substrate class hitherto unreactive catalysis) at pressure first time. In manner, late-stage modification isotope labeling amides, common subunits biologically compounds, can be realized through using first-row transition metal based on abundant copper. Preliminary mechanistic experiments indicate operates via an iminopyridine-mediated proximity effect. We hypothesize coordination alcohol as proton source copper(I) facilitates overall reactions rapid proto-decupration step.

Язык: Английский

Процитировано

1
Stereoconvergent reduction of alkenes using a repurposed iron-based dioxygenase DOI

Zicong Wan,

Xuan Zhang,

Helin Zhuang

и другие.

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Апрель 14, 2025

Язык: Английский

Процитировано

0
Mn(I)‐NNSe Pincer Complex Catalyzed Regioselective Synthesis of Bisindolylmethanes under Base and Solvent‐Free Conditions DOI
Suman Mahala, P S Rakesh, Sohan Singh

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 23, 2025

Abstract Here, we present a catalytic, regioselective synthesis of bisindolylmethanes through the reaction indoles and benzyl alcohol derivatives mediated by metal‐ligand cooperative catalysis. The is catalyzed an earth‐abundant manganese‐NNSe pincer complex without need for base, solvent, additives, or hydrogen acceptors yielding water dihydrogen as environmentally friendly by‐products. Notably, C‐3 N ‐alkylation indole, commonly observed in similar reactions were not detected. Mechanistic studies suggest that catalysis Mn(I)‐NNSe initiates conversion to benzaldehyde elimination, which subsequently facilitates bisindolylmethane derivatives. To highlight practical utility this method, wide range substrates can be activated with low catalyst loading under mild conditions.

Язык: Английский

Процитировано

0
Selective Functionalization of Alkenes and Alkynes by Dinuclear Manganese Catalysts DOI
Fei Wang,

Guichao Dong,

Suqi Yang

и другие.

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Окт. 2, 2024

ConspectusAlkenes and alkynes are fundamental building blocks in organic synthesis due to their commercial availability, bench-stability, easy preparation. Selective functionalization of alkenes is a crucial step for the value-added compounds. Precise control over these reactions allows efficient construction complex molecules with new functionalities. In recent decades, second- third-row precious transition metal catalysts (palladium, platinum, rhodium, ruthenium) have been pivotal development metal-catalyzed synthetic methodology. These metals exhibit excellent catalytic activity selectivity, enabling functionalized molecules. However, recovery reuse long challenge this field. years, exploration earth-abundant has interested both academic industrial researchers. The such systems offers promising approach overcome limitations catalysts. For example, manganese third most naturally abundant minimal toxicity biocompatibility. It exhibits good several reactions, including C-H bond functionalization, selective reduction, radical reactions. This Account outlines our progress dinuclear catalysis alkynes. We established elementary manganese(I)-catalysis transmetalation R-B(OH)

Язык: Английский

Процитировано

2
A ligand-assisted proximity effect allows for H2-driven copper hy-dride chemistry under mild conditions DOI Creative Commons

Mahadeb Gorai,

Philipp Rotering,

J. Franzen

и другие.

Опубликована: Окт. 16, 2024

A bifunctional copper(I)/N-heterocyclic carbene complex bearing a highly basic 2-iminopyridine subunit effects variety of copper(I) hydride-based reductive transformations at low H2 pressure. The catalyst allows for the first time to employ only catalytic amounts alkoxide additive and is with highest reactivity towards re-ported so far. We can demonstrate that efficient alkyne semihydrogenations, conjugate reductions as well 1,2-reductions carbonyl compounds be carried out very new protocol circumvents need previously required high-pressure equipment. At same time, use iminopyridine-based ligand tolerance an unprecedented functional groups in realm copper(I)-catalyzed hydrogenations. possible working model featuring iminopyridine-mediated proximity effect coordinates key close reactive cop-per(I) center proposed account observed significant rise reactivity. Mechanistic studies directed support-ing this current hypothesis are presented.

Язык: Английский

Процитировано

1
Recent Advances in Nonprecious Metal Catalysis DOI
David J. Bernhardson, Aran K. Hubbell, Robert A. Singer

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер unknown

Опубликована: Дек. 7, 2024

As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight practical advancements. We seek raise awareness both current art and need continue development toward broader applications earth-abundant metals chemical pharmaceutical industries.

Язык: Английский

Процитировано

1
Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation DOI Creative Commons
Arnaud Clerc,

M. Humbert,

Sonia Mallet‐Ladeira

и другие.

ChemistryEurope, Год журнала: 2024, Номер 3(1)

Опубликована: Ноя. 12, 2024

Abstract With the aim to explore metal‐ligand cooperation across Pd−S linkages, we designed a quinoline‐based PNS tridentate ligand and prepared Pd(II) complexes thereof. Optimal solubility stability of dicationic complex [(PNS)Pd(II)] 2 2+ IV were achieved with B(C 6 F 5 ) 4 – as counter‐anion. It adopts thiolate‐bridged dimeric structure (PdS) core, but readily activates hydrosilanes linkage. The resulting mononuclear hydride [(PNS SiR3 )Pd(II)H] + VI was characterized by multi‐nuclear NMR spectroscopy Si−H bond coordination/activation studied computationally. Complex found efficiently catalyze hydrosilylation alkynes, internal well terminal, good stereo regioselectivity.

Язык: Английский

Процитировано

0