Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1691 - 1691
Published: Jan. 1, 2024
Language: Английский
Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1691 - 1691
Published: Jan. 1, 2024
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9241 - 9251
Published: March 19, 2024
Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant
Language: Английский
Citations
19Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 27, 2025
The absolute and relative configurations of bioactive chiral molecules are typically relevant to their biological properties. It is thus highly important desirable construct all possible stereoisomers a lead candidate or given natural compound. Synergistic dual catalysis has been recognized as reliable synthetic strategy for variety predictable stereodivergent transformations. Despite the impressive progress made in this field, carbon-carbon bond-formation reactions involving stabilized nucleophiles remain elusive. Herein, we report an iridium- magnesium-catalyzed one-pot sequential allylic alkylation/nucleophilic alkylation cascade process synthesis four 3,3'-disubstituted oxindoles through three-component reaction. A diverse array products readily prepared with high functional group compatibility good yields excellent diastereo- enantioselectivities. Subsequently, total spirooxindole alkaloid trigolutes B D accomplished concise unified route using same set starting materials.
Language: Английский
Citations
2Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)
Published: March 21, 2024
Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.
Language: Английский
Citations
14Angewandte 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
11Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5788 - 5793
Published: June 27, 2024
Stereocontrolled oxa-Michael additions are challenging, given the high reversibility of process, which ultimately leads to racemization newly formed stereocenters. When iron-catalyzed borrowing hydrogen from allylic alcohols was combined with a stereocontrolled organocatalytic addition, wide array chiral tetrahydropyrans were efficiently prepared. The reaction could be performed in diastereoselective manner pre-existing stereocenters or enantioselectively achiral substrates. key success reactivity iron complex, selective for alcohol dehydrogenation and irreversibly led final product.
Language: Английский
Citations
6Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 10135 - 10145
Published: Jan. 1, 2024
A stereodivergent synthesis of chiral ζ-hydroxy amino esters containing 1,6-stereocenters and a unique β,γ-unsaturation was developed through asymmetric Cu/Ru relay catalysis to conduct the borrowing hydrogenation/1,6-Michael addition protocol.
Language: Английский
Citations
4ChemCatChem, Journal Year: 2024, Volume and Issue: unknown
Published: July 2, 2024
Abstract In the quest for more rapid and eco‐compatible preparation of complex molecules from widely available ones, borrowing hydrogen is one most elegant manners to directly functionalize alcohols. Such catalytic cycles reduce synthetic cost, avoid waste additional steps associated with adjusting redox state functionalization carbon chains. this field, last ten years have seen development general strategies control absolute stereochemistry created molecules. This enantiocontrol can arise three distinct cycle, namely initial dehydrogenation, carbonyl or final back‐transfer. review presents different enantioselective approaches developed according these principles highlights great potential transformations, current limitations future challenges.
Language: Английский
Citations
4Synthesis, Journal Year: 2024, Volume and Issue: 56(22), P. 3349 - 3364
Published: March 5, 2024
Abstract Transition-metal-catalyzed asymmetric allylic substitution reactions represent a hot research topic in the field of synthesis, with significant progress having been made. Among diverse catalysis systems, relay enables sequential activation multiple steps one pot and rapid construction chiral centers, providing simple powerful platform for organic synthesis. Recently, has successfully applied to reactions, variety challenging transformations have realized. This Short Review summarizes related on based over last decade. 1 Introduction 2 The General Transformation Model 3 Allylation Relays Further Reaction 4 Initial 5 Conclusion Outlook
Language: Английский
Citations
4Catalysts, Journal Year: 2025, Volume and Issue: 15(2), P. 151 - 151
Published: Feb. 6, 2025
A novel sequential one-pot bimetallic catalytic system combining Fe(III)-catalyzed alkynylation and a Rh(I)-catalyzed [2+2+2] reaction was successfully developed. The σ-Lewis acid properties of iron (III) the π-Lewis rhodium (I) catalysts were unified in an unprecedented intermolecular alkynylation/cyclotrimerization process. Using this unique Fe/Rh relay system, variety benzo pyrridinoisoindolinone derivatives obtained under mild conditions from easily available N-(propargyl) hydroxy aminals, as simplest N-acyliminium ion precursors, several alkynes.
Language: Английский
Citations
0Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 20, 2025
An enantioselective manganese(I)-catalyzed formal anti-Markovnikov hydroalkoxylation of racemic allylic alcohols has been developed using a chiral N6-type macrocyclic ligand, affording wide range γ-alkoxypropyl in high isolated yields with excellent enantioselectivities. The synthetic utility this protocol was further proven by gram-scale synthesis γ-alkoxypropanol 3n and derivatization 3a to drug molecule, (S)-dapoxetine, for the treatment premature ejaculation erectile dysfunction. Mechanistic studies support that reaction proceeds via hydrogen-borrowing cascade pathway.
Language: Английский
Citations
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