Mechanism of Iron-Catalyzed Oxidative α-Amination of Ketones with Sulfonamides DOI Creative Commons

Gloria M. Parrales,

Nina C. Hollin,

Fubin Song

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12462 - 12466

Published: Aug. 16, 2024

We report the mechanism of iron-catalyzed oxidative α-amination ketones with sulfonamides. Using linear free energy relationships, competition experiments, and identification reaction intermediates, we have found that this proceeds through rate-limiting electron transfer to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) from an iron enolate in process forming α-DDQ adduct. The adduct then serves as electrophile for substitution sulfonamide nucleophiles, accelerated by additional DDQ. This mechanistic study rules out formation α-carbocation intermediate purely radical hypotheses.

Language: Английский

Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization DOI
Yafia Kousin Mirza, Partha Sarathi Bera, Sachin Balaso Mohite

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4290 - 4317

Published: Jan. 1, 2024

Nickel-catalyzed hydrofunctionalization of π-substrates is a possibly effective method to synthesize several value-added molecular architectures. This review covers the NiH catalyzed reactions alkenes, alkynes and allenes.

Language: Английский

Citations

6
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

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

Citations

0
Mechanism of Iron-Catalyzed Oxidative α-Amination of Ketones with Sulfonamides DOI Creative Commons

Gloria M. Parrales,

Nina C. Hollin,

Fubin Song

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12462 - 12466

Published: Aug. 16, 2024

We report the mechanism of iron-catalyzed oxidative α-amination ketones with sulfonamides. Using linear free energy relationships, competition experiments, and identification reaction intermediates, we have found that this proceeds through rate-limiting electron transfer to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) from an iron enolate in process forming α-DDQ adduct. The adduct then serves as electrophile for substitution sulfonamide nucleophiles, accelerated by additional DDQ. This mechanistic study rules out formation α-carbocation intermediate purely radical hypotheses.

Language: Английский

Citations

0