Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1691 - 1691
Published: Jan. 1, 2024
Language: Английский
Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206
Published: Jan. 1, 2024
This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.
Language: Английский
Citations
15
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)
Published: May 16, 2024
Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.
Language: Английский
Citations
11
Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5758 - 5763
Published: July 1, 2024
Anthrones are key structural motifs in many natural products and pharmaceutical chemicals. However, due to its unique tricyclic aromatic structure, the synthetic space for development of chiral anthrone derivatives is largely limited. By utilizing potential copper-catalyzed remote asymmetric yne-allylic substitution reaction, we describe first example highly regio- enantioselective on various esters with anthrones under a mild reaction condition, which afforded range enantioenriched 1,3-enynes exhibiting broad functional group tolerance across 51 examples.
Language: Английский
Citations
7
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
Citations
4
Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 24, 2025
Comprehensive Summary Nitrogen‐containing bridged‐heterocycles and indoles are key subunits of many natural products pharmacologically active molecules. We herein present a bimetallic Cu/Ir catalyzed asymmetric allylation ketimine esters ( E )‐4‐indolyl allyl carbonates followed by acid‐promoted Pictet‐Spengler cyclization sequences, enabling stereodivergent synthesis chiral indole fused 9‐azabicyclo[4.2.1]nonanes containing an eight‐membered ring with one tertiary two quaternary stereogenic centers. This one‐pot sequential protocol features step economy, good substrate tolerance, excellent stereoselective control.
Language: Английский
Citations
0
Trends in Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 1, 2024
Language: Английский
Citations
3
Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown
Published: Dec. 13, 2024
Abstract A synergistic Pd/Cu catalyst system has been developed for stereodivergent transformation of Morita‐Baylis‐Hillman (MBH) carbonates and Schiff bases derived from simple amino acids to afford a series optically active β‐branched γ‐methyleneglutamic acid derivatives with adjacent tertiary/tertiary quaternary/tertiary stereocenters in high yields (up 96 %) excellent diastereo‐ enantioselectivities (>20/1 dr >99 % ee most cases) under mild conditions. The use SKP ligand is disclosed be crucial the success transformation, particular allowing reaction proceed at low loading (0.02 mol Pd 0.08 Cu). efficiency catalysis was attributed formation intimate ion pair complex A1 , composed Pd‐phosphonium cation t ‐butoxide anion, which would facilitate subsequent deprotonation C−C coupling events. All four stereoisomers glutamic were readily prepared by permutation enantiomers. Synthetic utility methodology exemplified efficient synthesis fused pyrrolooxazolidinone three contiguous chiral centers, highlighting power asymmetric allylic alkylation MBH carbonates.
Language: Английский
Citations
3
Molecular Catalysis, Journal Year: 2025, Volume and Issue: 573, P. 114819 - 114819
Published: Jan. 6, 2025
Language: Английский
Citations
0
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
Citations
2
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 11, 2024
Chiral 2-azetines and allenes are highly valuable structural units in natural products useful chemicals. However, enantioselective synthesis of both has been extremely challenging. Herein, we present asymmetric construction chiral (70-98 % yields up to 96 ee) through phosphine-catalyzed [2+2] annulation yne-enones with sulfamate-derived cyclic imines. These were easily transformed into upon treatment Et
Language: Английский
Citations
1