Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation DOI
Qiang Wu, Peng Hu

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1595 - 1605

Published: Feb. 3, 2024

Abstract Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation alkoxy radicals through chlorine radical‐induced radical formation, followed β ‐scission and trapping resulting carbon with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). reaction exhibits broad substrate scope (40 examples), including primary secondary that are prone to oxidation combination TEMPO iron. Mechanistic investigations have revealed enhanced coordination chloride ion center inhibits OH process, thereby enabling tolerance alcohols.

Language: Английский

Site- and Stereoselective Synthesis of Alkenyl Chlorides by Dual Functionalization of Internal Alkynes via Photoredox/Nickel Catalysis DOI

Liping Huo,

Xiaofang Li,

Yaheng Zhao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9876 - 9885

Published: April 18, 2023

Herein, we report a redox-neutral and atom-economical protocol to synthesize valuable alkenyl chlorides from unactivated internal alkynes abundant organochlorides via photoredox nickel catalysis. This enables the site- stereoselective addition of chlorine photoelimination-initiated sequential hydrochlorination/remote C-H functionalization. The is compatible with wide range medicinally relevant heteroaryl, aryl, acid, alkyl for efficiently producing γ-functionalized chlorides, exhibiting excellent regioselectivities stereoselectivities. Late-stage modifications synthetic manipulations products preliminary mechanistic studies are also presented.

Language: Английский

Citations

27

The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail? DOI
Felix Glaser,

Akin Aydogan,

Benjamin Elias

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215522 - 215522

Published: Nov. 9, 2023

Language: Английский

Citations

27

Radical Phosphorylation of Aliphatic C–H Bonds via Iron Photocatalysis DOI

Guang-Da Xia,

Zi‐Kui Liu,

Yulian Zhao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(28), P. 5279 - 5284

Published: July 11, 2023

The synthesis of tertiary phosphines(III) has been a long-standing challenge in synthetic chemistry because inevitable issues including harsh conditions, sensitive organometallic reagents, and prefunctionalized substrates traditional synthesis. Herein, we report strategically novel C(sp3)-H bond phosphorylation that enables the assembly structurally diverse from industrial phosphine(III) sources under mild photocatalytic conditions. merger ligand-to-metal charge transfer (LMCT) FeCl3 with hydrogen atom-transfer (HAT) process is key for generation alkyl radicals hydrocarbons. Strikingly, this catalytic system can be successfully applied polymerization electron-deficient alkenes.

Language: Английский

Citations

23

Visible-light induced direct C(sp3)–H functionalization: recent advances and future prospects DOI
Jia‐Lin Tu, Yining Zhu, Pengcheng Li

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5278 - 5305

Published: Jan. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Language: Английский

Citations

15

Iron photocatalysis via Brønsted acid-unlocked ligand-to-metal charge transfer DOI Creative Commons
Xiaoyu Jiang, Yu Lan,

Yudong Hao

et al.

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

Published: July 20, 2024

Abstract Reforming sustainable 3d-metal-based visible light catalytic platforms for inert bulk chemical activation is highly desirable. Herein, we demonstrate the use of a Brønsted acid to unlock robust and practical iron ligand-to-metal charge transfer (LMCT) photocatalysis multifarious haloalkylcarboxylates (C n X m COO − , = F or Cl) produce C radicals. This process enables fluoro-polyhaloalkylation non-activated alkenes by combining easily available Selectfluor as fluorine source. Valuable alkyl fluorides including potential drug molecules can be obtained through this protocol. Mechanistic studies indicate that real light-harvesting species may derive from in situ-assembly Fe 3+ H + acetonitrile solvent, which indeed increases efficiency LMCT between center via hydrogen-bond interactions. We anticipate acid-unlocked platform would an intriguing option execute compounds.

Language: Английский

Citations

14

Iron-catalyzed fragmentation-alkynylation, -alkenylation and -alkylation cascade enabled by photoinduced ligand-to-metal charge transfer DOI

Yining Zhu,

Han Gao, Jia‐Lin Tu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1729 - 1735

Published: Jan. 1, 2024

An iron-catalyzed fragmentation alkynylation, alkenylation and alkylation enabled by photoinduced ligand-to-metal charge transfer (LMCT)processis herein reported.

Language: Английский

Citations

11

Discovery and mechanistic investigation of photoinduced sp3 C–H activation of hydrocarbons by the simple anion hexachlorotitanate DOI Creative Commons
Grace B. Panetti, Qiaomu Yang, Michael R. Gau

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(4), P. 853 - 866

Published: March 18, 2022

Language: Английский

Citations

33

C–C bond formationviaphotocatalytic direct functionalization of simple alkanes DOI Creative Commons
Álvaro Velasco‐Rubio, Pol Martínez-Balart, Andrés M. Álvarez‐Constantino

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(62), P. 9424 - 9444

Published: Jan. 1, 2023

This article reviews the methodologies available to achieve C–C bond formation via photocatalytic and photo-electrocatalytic direct functionalization of simple alkanes.

Language: Английский

Citations

19

Unraveling the Prominent Existence of Trace Metals in Photocatalysis: Exploring Iron Impurity Effects DOI
Yahao Huang, Miao Wang, Wei Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4156 - 4164

Published: March 7, 2024

Metal impurities can complicate the identification of active catalyst species in transition metal catalysis and electrocatalysis, potentially leading to misleading findings. This study investigates influence on photocatalysis. Specifically, photocatalytic reaction inert alkanes using chlorides without use an external photocatalyst was studied, achieving successful C(sp

Language: Английский

Citations

8

Iron-Catalyzed Photochemical Synthesis of Sulfinamides from Aliphatic Hydrocarbons and Sulfinylamines DOI

Guang-Da Xia,

Run Li, Long Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3703 - 3708

Published: April 26, 2024

An iron-catalyzed photochemical sulfinamidation of hydrocarbons with

Language: Английский

Citations

8