Asymmetric 1,2‐Migration at Vicinal Tetrasubstituted Stereocenters Constructed from α‐Keto Imines

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 9, 2024

A carbonyl-assisted asymmetric 1,2-migratory allylation through in situ generation of vicinal tetrasubstituted stereocenters is reported to access enantiopure α-amino ketones and amino alcohols with excellent yields diastereoselectivities. In a remarkable divergence, despite higher steric hindrance, the exclusively occurs on over imines first step, followed by face-selective 1,2-allyl transfer, thus highlighting an exciting interplay between two distinct electrophiles. The methodology distinguishes itself its adaptability gram-scale synthesis, showcasing broad functional-group tolerance stereodivergence. Density functional theory (DFT) analysis led deeper understanding selectivity mechanistic framework. Highlighting transformative potential, method was applied total synthesis hapalindole alkaloids.

Language: Английский

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Sequential Cu-Borylation Strategy for a Stereodivergent Synthesis of Functionalized Cyclohexanones

Synfacts, Journal Year: 2024, Volume and Issue: 20(03), P. 0280 - 0280

Published: Feb. 14, 2024

Key words copper catalysis - borylation desymmetrization

Language: Английский

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Asymmetric 1,2‐Migration at Vicinal Tetrasubstituted Stereocenters Constructed from α‐Keto Imines

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 9, 2024

Abstract A carbonyl‐assisted asymmetric 1,2‐migratory allylation through in situ generation of vicinal tetrasubstituted stereocenters is reported to access enantiopure α‐amino ketones and amino alcohols with excellent yields diastereoselectivities. In a remarkable divergence, despite higher steric hindrance, the exclusively occurs on over imines first step, followed by face‐selective 1,2‐allyl transfer, thus highlighting an exciting interplay between two distinct electrophiles. The methodology distinguishes itself its adaptability gram‐scale synthesis, showcasing broad functional‐group tolerance stereodivergence. Density functional theory (DFT) analysis led deeper understanding selectivity mechanistic framework. Highlighting transformative potential, method was applied total synthesis hapalindole alkaloids.

Language: Английский

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HTE-Enabled Development of an Ene-Reductase-Catalyzed Desymmetrization: Remote Control of All-Carbon Quaternary γ-Centers

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

We report the remote stereocontrol of all-carbon quaternary γ-centers via an ene-reductase (ERED)-catalyzed desymmetrization prochiral cyclohexadienones. By leveraging high-throughput experimentation (HTE) protocols, we were able to rapidly identify EREDs capable desymmetrizing both spirocyclic cyclohexadienones and non-spirocyclic 2,6-disubstituted cyclohexadienone substrates in up 85% yield with excellent levels stereoselectivity (up >99% ee >20:1 dr) under mild reaction conditions.

Language: Английский

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