Difluorocarbene-induced [1,2]- and [2,3]-Stevens rearrangement of tertiary amines

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 5, 2024

The [1,2]- and [2,3]-Stevens rearrangements are one of the most fascinating chemical bond reorganization strategies in organic chemistry, they have been demonstrated a wide range applications, representing fundamental reaction tactic for synthesis nitrogen compounds community. However, their applicabilities limited by scarcity efficient, general, straightforward methods generating ammonium ylides. Herein, we report general difluorocarbene-induced tertiary amine-involved stemmed from situ generated difluoromethyl ylides, which allows versatile amines bearing either allyl, benzyl, or propargyl groups, resulting corresponding products under same conditions with way. Broad substrate scope, simple operation, mild late-stage modification natural highlight advantages this strategy, meanwhile, rearrangement is believed to bring opportunities transformations ylides assembly valuable amino acids. This will further enrich repertoire difluorocarbene species, facilitate development reactions involving salts, provide an avenue type reactions.

Language: Английский

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A Metal-Catalyzed Tunable Reaction of Ylides with Hydroxylamine Derivatives

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

In this work, a tunable reaction of metal acyl nitrene with ylides is reported for the divergent synthesis enamides and α,α-dicarbonyl phosphorus ylides. The featured mild conditions, good efficiency, broad generality. particular, resulting could be structurally elaborated into potential useful scaffolds. Mechanism investigation suggests that formation was ascribed to nucleophilic substitution ferric sulfur It believed represents an initial example preparing from iron-catalyzed transfer.

Language: Английский

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Ligand-controlled divergent asymmetric C(sp3)−H and C(sp3)−O insertion via vinyl cations

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 2, 2025

The insertion of either C-H bond or C-O via cleavage has proven to be a very attractive strategy for the construction C-C and bonds in organic synthesis. However, such divergent catalytic asymmetric reactions selective formation C(sp3)-H formal C(sp3)-O products from same precursors are rarely explored. Herein, we report ligand-controlled reaction vinyl cations by non-diazo approach, leading practical atom-economical assembly range chiral spiro fused polycyclic pyrroles generally moderate excellent yields with chemo- enantioselectivities. Importantly, this protocol not only represents rare example successful reaction, but also constitutes an enantioselective 1,6-C-H carbenoid into acetals approach.

Language: Английский

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Organocatalytic Enantioselective [1,2]-Stevens Rearrangement of Azetidinium Salts

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 9063 - 9067

Published: June 7, 2024

The first organocatalyzed enantioselective [1,2]-Stevens rearrangement is reported. 4-Alkylideneproline derivatives are produced in up to 86% yield and 90:10 er, with recrystallization enhancing er >99.5:0.5. Product configuration was opposite that predicted by existing stereochemical models for this organocatalyst class, DFT calculations revealed a novel mode of asymmetric induction. adaptability catalytic strategy rearrangements other heterocyclic amines demonstrated.

Language: Английский

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Cu(i)-catalyzed dearomatizing cascade of thiazoles using two molecules of an α-aryl-α-diazoester: a novel approach for the synthesis of densely substituted 4-thiazolines

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(21), P. 6117 - 6125

Published: Jan. 1, 2024

A novel copper( i )-catalyzed cascade reaction has been devised for the functionalization of thiazoles, which employs two molar equivalents an α-aryl-α-diazoester.

Language: Английский

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