Regio- and stereoselective syntheses of chiral α-quaternary (Z)-trisubstituted allylic amino acidsviasynergistic Pd/Cu catalysis

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(18), P. 2632 - 2635

Published: Jan. 1, 2023

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed the synthesis α-quaternary (Z)-trisubstituted amino acids under mild conditions. This methodology features broad substrate compatibilities in yields up to 87% and 94% ee. A facile scale-up straightforward conversion 1,2,3,5-tetrasubstituted pyrrole 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies synthetic utility this method.

Language: Английский

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Rational Design and Stereodivergent Construction of Enantioenriched Tetrahydro-β-Carbolines Containing Multistereogenic Centers

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29928 - 29942

Published: Oct. 17, 2024

Chiral tetrahydro-β-carbolines, as one of the most intriguing subtypes indole alkaloids, have emerged privileged units in plenty natural products and biologically active molecules with an impressive range bioactive properties. However, stereodivergent construction these valuable skeletons containing multistereogenic centers from readily available starting materials remains very challenging, especially, view introduction axial chirality. Herein, we developed efficient method toward enantioenriched tetrahydro-β-carbolines tryptophan-derived aldimine esters allylic carbonates under mild reaction conditions. The proceeds a sequential fashion involving synergistic Cu/Ir-catalyzed allylation Brønsted acid-promoted stereospecific Pictet–Spengler reaction, affording wide chiral bearing up to four stereogenic good yields excellent stereoselectivity control. When N-aryl-substituted were utilized, notably, unique C–N heterobiaryl axis could be simultaneously constructed formation third point center last cyclization step through dynamic kinetic resolution (DKR). Computational mechanistic studies established plausible mechanism for dual asymmetric succeeding protonation-assisted complete annulation. Structure–activity relationship analyses unveil origins stereochemistry building three centers.

Language: Английский

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Ni/Cu Dual‐Catalyzed Propargylation for the Stereodivergent Synthesis of Methohexital

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 25, 2024

The development of efficient methodologies for the controlled manufacture specific stereoisomers bearing quaternary stereocenters has prompted advances in a variety scientific disciplines including pharmaceutical chemistry, materials science, and chemical biology. However, complete control absolute relative stereochemical configurations alkyne derivatives remains an unmet synthetic challenge. Herein, Ni/Cu dual-catalyzed asymmetric propargylic substitution reaction is presented to produce propargylated products with all-carbon high yields significant diastereo- enantioselectivities (up >20:1 dr, >99% ee). synthesis all variants methohexital, widely used sedative-hypnotic drug, exemplifies efficacy stereodivergent propargylation.

Language: Английский

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Synthesis of Medium-Sized Rings by Z-Retentive Asymmetric Allylic Substitution-Enabled Intermolecular Cascade Cyclization under Iridium/Cinchona Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15743 - 15750

Published: Oct. 9, 2024

Medium-sized rings are important structural units in organic molecules of significant interest. However, their efficient synthesis, especially a highly enantioselective manner, has been formidable challenge. Herein, we report an synthesis medium-sized aza-rings by Z-retentive asymmetric allylic substitution-enabled intermolecular cascade cyclization via iridium/cinchona dual catalysis. The reaction was performed under mild conditions and with good functional group tolerance. Various nine- to eleven-membered can be afforded moderate high yields (up 98%) enantioselectivities 93% ee). utilization both Z-linear dipole precursor binary catalyst is critical for the desired reactivity.

Language: Английский

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Stereodivergent dual catalysis in organic synthesis

Trends in Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

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