Observation of parallel intersystem crossing and charge transfer-state dynamics in [Fe(bpy)3]2+ from ultrafast 2D electronic spectroscopy DOI Creative Commons
Angela Lee, Minjung Son, Mawuli Deegbey

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 13140 - 13150

Published: Jan. 1, 2023

Transition metal-based charge-transfer complexes represent a broad class of inorganic compounds with diverse photochemical applications. Charge-transfer based on earth-abundant elements have been increasing interest, particularly the canonical [Fe(bpy)3]2+. Photoexcitation into singlet metal-ligand charge transfer (1MLCT) state is followed by relaxation first to ligand-field manifold and then ground state. While these dynamics well-studied, processes within MLCT that facilitate and/or compete more elusive. We applied ultrafast two-dimensional electronic spectroscopy (2DES) disentangle immediately following excitation this compound. First, ascribed out initially formed 1MLCT was found correlate inertial response time solvent. Second, additional dimension 2D spectra revealed peak consistent ∼20 fs → 3MLCT intersystem crossing process. These two observations indicate complex simultaneously undergoes direct conversion state(s). Resolution parallel pathways in prototypical highlights ability 2DES deconvolve otherwise obscured excited-state complexes.

Language: Английский

Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis DOI Creative Commons
Feng‐Hua Zhang,

Xiaochong Guo,

Xianrong Zeng

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Language: Английский

Citations

70
Photochemical Synthesis of Succinic Ester-Containing Phenanthridines from Diazo Compounds as 1,4-Dicarbonyl Precursors DOI

Hai‐Bing Ye,

Xu-Yu Zhou,

Lei Li

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 6018 - 6023

Published: Aug. 10, 2022

We disclosed herein a straightforward photochemical method for the construction of phenanthridines containing synthetically useful succinate unit. The reaction occurred under visible-light irradiation with cheap eosin Y Na as photoredox catalyst and diazo compound precursor. Under optimal conditions, wide range were obtained in moderate to good yields. Note that units final heterocycles could be easily transformed into many valuable structures, such γ-butyrolactone, dihydrofuran-2(3H)-one, tetrahydrofuran. Mechanistic experiments performed support proposed mechanism.

Language: Английский

Citations

43
Visible light-mediated NHCs and photoredox co-catalyzed radical 1,2-dicarbonylation of alkenes for 1,4-diketones DOI
Lihong V. Wang, Jiaqiong Sun,

Jiuli Xia

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(10), P. 1938 - 1944

Published: Sept. 2, 2022

Language: Английский

Citations

42
Piezocatalyzed Decarboxylative Acylation of Quinoxalin-2(1H)-ones Using Ball Milling DOI
Yu He, Gefei Wang, Wenbo Hu

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(3), P. 910 - 920

Published: Jan. 11, 2023

The first piezochemically driven decarboxylative coupling of the C–H bond was developed. agitation BaTiO3 via ball milling converts mechanical energy into electrical potential, leading to production a benzoyl radical single-electron transfer pathway analogous photocatalytic reaction. This mechanoredox catalytic strategy synthesize C3-acylated quinoxalin-2(1H)-ones requires no solvent, short reaction time, and simple handling skills, exhibiting promising potential in large-scale chemical manufacturing.

Language: Английский

Citations

32
Recent advances in three-component radical acylative difunctionalization of unsaturated carbon–carbon bonds DOI
Jiaqiong Sun, Lihong V. Wang, Guangfan Zheng

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(18), P. 4488 - 4515

Published: Jan. 1, 2023

This review highlights the recent advances in radical acylated difunctionalization of unsaturated carbon–carbon bonds and focuses on mechanistic insights these transformations.

Language: Английский

Citations

31
Carbon monoxide enabling synergistic carbonylation and (hetero)aryl migration DOI
Yuanrui Wang,

Hefei Yang,

Yan Zheng

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(10), P. 1065 - 1075

Published: Aug. 6, 2024

Language: Английский

Citations

13
Unlocking the Nucleophilicity of Strong Alkyl C–H Bonds via Cu/Cr Catalysis DOI Creative Commons
Pan Peng,

Yifan Zhong,

Cong Zhou

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(4), P. 756 - 762

Published: March 27, 2023

Direct functionalization of inert C-H bonds is one the most attractive yet challenging strategies for constructing molecules in organic chemistry. Herein, we disclose an unprecedented and Earth abundant Cu/Cr catalytic system which unreactive alkyl are transformed into nucleophilic alkyl-Cr(III) species at room temperature, enabling carbonyl addition reactions with strong bonds. Various aryl alcohols furnished under mild reaction conditions even on a gram scale. Moreover, this new radical-to-polar crossover approach further applied to 1,1-difunctionalization aldehydes alkanes different nucleophiles. Mechanistic investigations reveal that aldehyde not only acts as reactant but also serves photosensitizer recycle Cu Cr catalysts.

Language: Английский

Citations

22
Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles† DOI
Wei Li,

Donghao Jiang,

Cheng Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(23), P. 3419 - 3432

Published: July 27, 2023

Comprehensive Summary Transition metal‐catalyzed carbonylation reactions represent a direct and atom‐economical approach to synthesize carbonyl compounds or their derivatives by using CO as cheap readily available C1 feedstock. While of C(sp 2 )‐hybridized electrophiles ( e.g ., aryl halides) is well developed, less reactive unactivated alkyl remains challenging. Recently, the use earth‐abundant base metals including Cu, Co, Mn, Fe, Ni catalysts has enabled advances in carbonylative coupling for approaching diverse derivatives, notably, some which are synthetic importance but difficult be synthesized through previous reported methods. Herein, we have summarized discussed these recent achievements base‐metal‐catalyzed C—C, C—N, C—O, C—X other source.

Language: Английский

Citations

18
Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines DOI Creative Commons
Huan Meng, Jun-Song Jia, Pengfei Yang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: 16(10), P. 4442 - 4449

Published: Jan. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Language: Английский

Citations

1
Cooperative NHC and Photoredox Catalysis for the Synthesis of 1,4-Dicarbonyl Compounds via Diacylation of Alkenes DOI

Shihao Li,

Haojun Shu,

Sheng Wang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(31), P. 5710 - 5714

Published: Aug. 3, 2022

An intermolecular 1,2-diacylation of alkenes is disclosed via cooperative N-heterocyclic carbene and photoredox catalysis under the mediation PPh3 Cs2CO3. This protocol provides a practical approach for construction 1,4-dicarbonyl compounds toward novel diketone pharmaceutical derivatives. Furthermore, regioselective dicarbonyl can be synthesized by adding acyl azolium salt. Mechanistic investigations suggest that process was critical radical/radical cross coupling ketyl radicals with benzylic C-radicals.

Language: Английский

Citations

29