Cobalt-Catalyzed Carbon–Heteroatom Transfer Enables Regioselective Tricomponent 1,4-Carboamination DOI

Kaitong Zhuang,

Graham C. Haug, Yangyang Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8508 - 8519

Published: Feb. 21, 2024

Tricomponent cobalt(salen)-catalyzed carbofunctionalization of unsaturated substrates by radical-polar crossover has the potential to streamline access broad classes heteroatom-functionalized synthetic targets, yet reaction platform remained elusive, despite well-developed analogous hydrofunctionalizations mediated high-valent alkylcobalt intermediates. We report herein development a cobalt(salen) catalytic system that enables carbofunctionalization. The entails tricomponent decarboxylative 1,4-carboamination dienes and provides direct route aromatic allylic amines obviating preformed allylation reagents protection oxidation-sensitive amines. merges acridine photocatalysis with regioselective 1,4-carbofunctionalization facilitates radical polar phases coupling process, revealing critical roles reactants, as well ligand effects nature formal species on chemo- regioselectivity.

Language: Английский

Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer DOI Creative Commons
Filip S. Meger, John A. Murphy

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

Citations

29
Hydrogen-bond-acceptor ligands enable distal C(sp3)–H arylation of free alcohols DOI
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park

et al.

Nature, Journal Year: 2023, Volume and Issue: 622(7981), P. 80 - 86

Published: Sept. 6, 2023

Language: Английский

Citations

29
Ligand‐Enabled Palladium(II)‐Catalyzed Enantioselective β‐C(sp3)−H Arylation of Aliphatic Tertiary Amides** DOI
Chen‐Hui Yuan, Xiaoxia Wang, Lei Jiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 5, 2023

Amide is one of the most widespread functional groups in organic and bioorganic chemistry, it would be valuable to achieve stereoselective C(sp3 )-H functionalization amide molecules. Palladium(II) catalysis has been prevalently used C-H activation chemistry past decades, however, due weakly-coordinating feature simple amides, challenging their direct with enantiocontrol by PdII catalysis. Our group developed sulfoxide-2-hydroxypridine (SOHP) ligands, which exhibited remarkable activity Pd-catalyzed C(sp2 activation. In this work, we demonstrate that chiral SOHP ligands served as an ideal solution enantioselective amides. Herein, report efficient asymmetric /SOHP-catalyzed β-C(sp3 arylation aliphatic tertiary ligand plays a key role deprotonation-metalation step.

Language: Английский

Citations

25
Convergent and Efficient Total Synthesis of (+)-Heilonine Enabled by C–H Functionalizations DOI Creative Commons
Yuan Jin,

Sovanneary Hok,

John Bacsa

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 1825 - 1831

Published: Jan. 16, 2024

We report a convergent and efficient total synthesis of the C-nor D-homo steroidal alkaloid (+)-heilonine with hexacyclic ring system, nine stereocenters, trans-hydrindane moiety. Our features four selective C–H functionalizations to form key C–C bonds Stille carbonylative cross-coupling connect AB system DEF Nazarov cyclization construct five-membered C ring. These enabling transformations significantly reduced functional group manipulations delivered in 11 or 13 longest linear sequence (LLS) steps.

Language: Английский

Citations

14
Cobalt-Catalyzed Carbon–Heteroatom Transfer Enables Regioselective Tricomponent 1,4-Carboamination DOI

Kaitong Zhuang,

Graham C. Haug, Yangyang Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8508 - 8519

Published: Feb. 21, 2024

Tricomponent cobalt(salen)-catalyzed carbofunctionalization of unsaturated substrates by radical-polar crossover has the potential to streamline access broad classes heteroatom-functionalized synthetic targets, yet reaction platform remained elusive, despite well-developed analogous hydrofunctionalizations mediated high-valent alkylcobalt intermediates. We report herein development a cobalt(salen) catalytic system that enables carbofunctionalization. The entails tricomponent decarboxylative 1,4-carboamination dienes and provides direct route aromatic allylic amines obviating preformed allylation reagents protection oxidation-sensitive amines. merges acridine photocatalysis with regioselective 1,4-carbofunctionalization facilitates radical polar phases coupling process, revealing critical roles reactants, as well ligand effects nature formal species on chemo- regioselectivity.

Language: Английский

Citations

13