Electrooxidative Pd-Catalyzed Remote Hydrofunctionalization of Alkenes with Nucleophiles DOI

Seungdae Park,

Baeho Yang,

Do‐Hyun Lee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15858 - 15868

Published: Oct. 11, 2024

The catalytic hydrofunctionalization of alkenes with nucleophiles via the generation carbocationic intermediates has been extensively studied as an efficient strategy for regioselective installation functional groups on alkene feedstocks. However, since established methods are confined to functionalization position where is originally located, it highly desirable develop a broadly applicable platform that offers alternative regioselectivity otherwise challenging achieve existing protocols. Herein, we report remote method enabled by electrooxidative palladium hydride catalysis. key success formation carbocation intermediate through mechanistic pathway, which involves chain-walking process followed anodic oxidation organopalladium species. This allows terminal and internal broad range oxygen, carbon, nitrogen, fluoride nucleophiles, including complex drug-like molecules.

Language: Английский

Regiodivergent and Enantioselective Synthesis of Cyclic Sulfones via Ligand‐Controlled Nickel‐Catalyzed Hydroalkylation DOI Creative Commons
Chao Fan, Uttam Dhawa, Deyun Qian

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: April 29, 2024

Abstract Cyclic sulfones have demonstrated important applications in drug discovery. However, the catalytic and enantioselective synthesis of chiral cyclic remains challenging. Herein, we develop nickel‐catalyzed regiodivergent hydroalkylation sulfolenes to streamline alkyl sulfones. The method has broad scope high functional group tolerance. regioselectivity can be controlled by ligands only. A neutral PYROX ligand favors C3‐alkylation whereas an anionic BOX C2‐alkylation. This control is kinetic origin as C2‐bound Ni intermediates are always thermodynamically more stable. Reactivity study a wide range relevant reveal I /Ni III cycle with II −H species resting state. regio‐ enantio‐determining step insertion this into 2‐sulfolene. work provides efficient for class organic compounds enhances mechanistic understanding Ni‐catalyzed stereoselective hydroalkylation.

Language: Английский

Citations

0
Construction of C5‐Indole Unnatural Amino Acid Motifs via Diastereoselective Pd(II)‐Catalyzed β‐C(sp3)‐H Functionalization DOI
Pooja Patel, Srinivasarao Arulananda Babu, Radha Tomar

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(25)

Published: May 4, 2024

Abstract We report the construction of C5‐indole unnatural amino acid derivatives via diastereoselective Pd(II)‐catalyzed prochiral β ‐C(sp 3 )‐H arylation racemic (DL), and enantiopure L‐ D‐carboxamides acids with 5‐iodoindoles. Independently, indole‐based compounds motifs are important small molecules in organic synthesis drug discovery research. This aimed to contribute enriching library derivatives. The examples motif‐installed comprising norvaline, phenylalanine, leucine, norleucine, 2‐aminooctanoic having anti‐ stereochemistry was accomplished. motif‐containing non‐ α ‐amino (aminoalkanoic acid) also reported. C−H reactions carboxamides 5‐iodoindoles afforded corresponding indole good diastereoselectivity ( anti , dr >95 : 5 enantiopurity er up 99 1). Removal directing group (8‐aminoquinoline), phthalimide preparation esters free group‐containing were shown. utility methodology shown by synthesizing pyrrolidone peptide molecules. major ) diastereomers ascertained from X‐ray structure a representative compound.

Language: Английский

Citations

0
Cobalt-Catalyzed Regio- and Enantioselective Hydroalkylation of 1,1-Disubstituted Styrenes DOI
Xi Lu, Lifeng Yan

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 2, 2024

Abstract The metal hydride catalyzed alkene hydroalkylation enables efficient alkyl–alkyl coupling, yielding structurally diverse chiral organic compounds. However, the control of stereochemical selectivity in still heavily relies on assistance substrate Lewis basic functional groups or polar heteroatom groups. We have recently developed a cobalt catalytic system and established paradigm enantioselective assisted by C–H···π noncovalent interactions. This approach asymmetric 1,1-disubstituted styrenes, thereby circumventing limitations imposed 1 Introduction 2 Reaction Development 3 Synthetic Applications 4 Mechanistic Investigation 5 Conclusion Future Outlook

Language: Английский

Citations

0
Multifunctionalization of Alkenyl Alcohols via a Sequential Relay Process DOI
Chong Liu, Ling Wang, Haibo Ge

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30733 - 30740

Published: Oct. 29, 2024

Aryl-substituted aliphatic amines are widely recognized as immensely valuable molecules. Consequently, the development of practical strategies for construction these molecules becomes increasingly urgent and critical. Here, we have successfully achieved multifunctionalization reactions alkenyl alcohols in a sequential relay process, which enables transformation patterns arylamination, deuterated methylenated arylamination to easy access multifarious arylalkylamines. Notably, novel functionalization mode carbonyl groups has been developed facilitate processes deuterium incorporation methylene introduction, thereby providing new means diverse transformations groups. This methodology displays wide tolerance toward functional groups, while also exhibiting good applicability across various skeletal structures alkenols amines.

Language: Английский

Citations

0
Palladium-catalyzed remote internal C(sp3)−H bond chlorination of alkenes DOI Creative Commons

Yao-Xin Wang,

Zhen Wang, Xiao‐Hui Yang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Dec. 5, 2024

Language: Английский

Citations

0
Facile construction of distal and diversified tertiary and quaternary stereocenters DOI Creative Commons
Chong Liu,

Robbie Ge,

Jun Chen

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(51)

Published: Dec. 12, 2024

Exploration of novel chiral pharmaceutical candidates is motivation to immersive efforts among synthetic chemists. Achieving skeletal construction and diversity in a highly efficient manner momentous goal the chemical society. Unfortunately, current methods for induction focus primarily on specific site. Herein, we realized asymmetric chain-walking arylation alkenyl alcohols multisite tertiary quaternary stereocenters high yields enantioselectivity. This new operation-friendly strategy carries substantial potential future industrialization.

Language: Английский

Citations

0
Electrooxidative Pd-Catalyzed Remote Hydrofunctionalization of Alkenes with Nucleophiles DOI

Seungdae Park,

Baeho Yang,

Do‐Hyun Lee

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 15858 - 15868

Published: Oct. 11, 2024

The catalytic hydrofunctionalization of alkenes with nucleophiles via the generation carbocationic intermediates has been extensively studied as an efficient strategy for regioselective installation functional groups on alkene feedstocks. However, since established methods are confined to functionalization position where is originally located, it highly desirable develop a broadly applicable platform that offers alternative regioselectivity otherwise challenging achieve existing protocols. Herein, we report remote method enabled by electrooxidative palladium hydride catalysis. key success formation carbocation intermediate through mechanistic pathway, which involves chain-walking process followed anodic oxidation organopalladium species. This allows terminal and internal broad range oxygen, carbon, nitrogen, fluoride nucleophiles, including complex drug-like molecules.

Language: Английский

Citations

0