Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Sept. 10, 2024

Abstract Different from the reported work focusing on construction of single P ‐ or C ‐stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo‐ and enantioselective reaction allenes, conjugated enynes 1,3‐dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3‐enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four ‐containing stereoisomers. present protocol features use only 3‐minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

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Enantioselective Palladium‐Catalyzed Directed Migratory Allylation of Remote Dienes

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(34)

Published: June 30, 2023

Abstract Chain walking has been an efficient route to realize the functionalization of inert C(sp 3 )−H bonds, but this strategy is limited mono‐olefin migration and functionalization. Herein, we demonstrate feasibility tandem directed simultaneous migrations remote olefins stereoselective allylation for first time. The adoption palladium hydride catalysis secondary amine morpholine as solvent critical achieving high substrate compatibility stereochemical control with method. protocol also applicable three vicinal bonds thus construct continuous stereocenters along a propylidene moiety via short synthetic process. Preliminary mechanistic experiments corroborated design dienes.

Language: Английский

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Stereodivergent 1,5-Conjugate Addition with Iminoesters via Pd/Cu Dual Catalysis

Synthesis, Journal Year: 2023, Volume and Issue: 56(22), P. 3412 - 3420

Published: Dec. 15, 2023

Abstract The first stereodivergent umpolung 1,5-conjugate addition reaction via synergistic Pd/Cu catalysts is reported. By dictating the absolute configuration of each chiral ligand ligated to corresponding metals, all four stereoisomers products are easily achieved. A series amino acid moieties introduced γ-position conjugated esters in high yields with excellent diastereoselectivities and enantioselectivities. downstream transformations highlight synthetic value method.

Language: Английский

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Transition Metal‐Catalyzed Migratory Tsuji‐Trost Reaction

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(22)

Published: Oct. 2, 2023

Abstract Beyond the scope of classical Tsuji‐Trost reaction, an alkene bearing a remote leaving group is not considered as potential substrate for allylation. The concept migratory reaction focuses on transformations with this type substrates. Two pathways including olefin migration and to form typical allyl intermediate following substitution have been explored demonstrate feasibility new concept.

Language: Английский

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Diastereoselective and Enantioselective Hydrophosphinylations of Conjugated Enynes, Allenes and Dienes via Synergistic Pd/Co Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Sept. 10, 2024

Different from the reported work focusing on construction of single P- or C-stereocenter via hydrophosphinylation unsaturated carbon bonds, highly diastereo- and enantioselective reaction allenes, conjugated enynes 1,3-dienes is achieved a designed Pd/Co dual catalysis newly modified masked phosphinylating reagent. A series allyl motifs bearing both tertiary C- P-stereocenter are prepared in generally good yields, >20 : 1 dr, rr 99 % ee. The unprecedented 1,3-enynes established to generate skeletons containing nonadjacent chiral axis. first stereodivergent also developed achieve all four P-containing stereoisomers. present protocol features use only 3-minutes time 0.1 catalyst, with observation up 730 TON. set mechanistic studies reveal necessity roles two metal catalysts corroborate synergistic process.

Language: Английский

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Palladium-catalyzed remote allylation of styrene derivatives: DFT calculations unraveling regioselectivity controlled by non-covalent interactions

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 555, P. 113905 - 113905

Published: Feb. 1, 2024

Language: Английский

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Construction of remote cyano-substituted quaternary carbon centers via nickel-catalyzed migratory hydrocyanation of unconjugated dienes

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(10), P. 3397 - 3405

Published: Aug. 21, 2024

Language: Английский

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