Asymmetric imino-acylation of alkenes enabled by HAT-photo/nickel cocatalysis DOI Creative Commons
Rui Wang, Chuan Wang

Chemical Science, Journal Year: 2023, Volume and Issue: 14(23), P. 6449 - 6456

Published: Jan. 1, 2023

By merging nickel-mediated facially selective aza-Heck cyclization and radical acyl C-H activation promoted by tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst, we accomplish an asymmetric imino-acylation of oxime ester-tethered alkenes with readily available aldehydes the source, enabling synthesis highly enantioenriched pyrrolines bearing acyl-substituted stereogenic center under mild conditions. Preliminary mechanistic studies support Ni(i)/Ni(ii)/Ni(iii) catalytic sequence involving intramolecular migratory insertion tethered olefinic unit into Ni(iii)-N bond enantiodiscriminating step.

Language: Английский

Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols DOI
Christian J. Oswood, David W. C. MacMillan

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 93 - 98

Published: Dec. 22, 2021

Traditional approaches to stereoselective synthesis require high levels of enantio- and diastereocontrol in every step that forms a new stereocenter. Here, we report an alternative approach, which the stereochemistry organic substrates is selectively edited without further structural modification, strategy with potential allow classes late-stage stereochemical manipulation provide access rare or valuable configurations. In this work, describe selective epimerization cyclic diols enabled by hydrogen atom transfer photocatalysis boronic acid mediated transient thermodynamic control, generating less stable cis products from otherwise favored trans isomers. A range substitution patterns ring sizes are amenable isomerization, including stereochemically complex polyols such as estriol, well syn anti acyclic vicinal diols. Moreover, has divergent saccharide anomers, providing distinct sugar isomers α- β-configured glycosides.

Language: Английский

Citations

74
Energy- and atom-efficient chemical synthesis with endergonic photocatalysis DOI
Huaiju Wang, Ya‐Ming Tian,

Burkhard König

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(10), P. 745 - 755

Published: Sept. 23, 2022

Language: Английский

Citations

60
Accelerated and Scalable C(sp3)–H Amination via Decatungstate Photocatalysis Using a Flow Photoreactor Equipped with High-Intensity LEDs DOI Creative Commons
Ting Wan, Zhenghui Wen, Gabriele Laudadio

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 8(1), P. 51 - 56

Published: Dec. 16, 2021

Carbon-nitrogen bonds are ubiquitous in biologically active compounds, prompting synthetic chemists to design various methodologies for their preparation. Arguably, the ideal approach is be able directly convert omnipresent C-H organic molecules, enabling even late-stage functionalization of complex scaffolds. While this has been thoroughly investigated C(sp

Language: Английский

Citations

57
Radical Hydro‐Fluorosulfonylation of Unactivated Alkenes and Alkynes DOI
Peng Wang, Honghai Zhang,

Mingqi Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 9, 2022

Abstract Recently, radical fluorosulfonylation is emerging as an appealing approach for the synthesis of sulfonyl fluorides, which are highly in demand various disciplines, particularly chemical biology and drug discovery. Here, we report first establishment hydro‐fluorosulfonylation alkenes, enabled by using 1‐fluorosulfonyl 2‐aryl benzoimidazolium (FABI) effective redox‐active precursor. This method provides a new facile aliphatic fluorides from unactivated can be further applied to late‐stage modifications natural products peptides, well ligation drugs combination with click chemistry. Remarkably, this system could enable alkynes, affording valuable alkenylsulfonyl fluoride rare, high Z ‐selectivity, normally less stable more challenging synthesize comparison E ‐configured products.

Language: Английский

Citations

54
Decatungstate-catalyzed radical disulfuration through direct C-H functionalization for the preparation of unsymmetrical disulfides DOI Creative Commons
Jingjing Zhang, Armido Studer

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

Published: July 6, 2022

Abstract Unsymmetrical disulfides are widely found in the areas of food chemistry, pharmaceutical industry, chemical biology and polymer science. Due importance such various fields, general methods for nondirected intermolecular disulfuration C-H bonds highly desirable. In this work, conversion aliphatic C(sp 3 )-H aldehydic 2 into corresponding C-SS with tetrasulfides (RSSSSR) as radical reagents is reported. The decatungstate anion ([W 10 O 32 ] 4− ) photocatalyst used C-radical generation via hydrogen atom transfer combination cheap sodium persulfate (Na S 8 oxidant. Herein a series valuable acyl alkyl disulfides, important precursors RSS-anions, unsymmetrical dialkyl synthesized using direct approach. To demonstrate potential method late-stage functionalization, approved drugs natural products were successfully functionalized.

Language: Английский

Citations

53
Brønsted acid-enhanced direct hydrogen atom transfer photocatalysis for selective functionalization of unactivated C(sp3)–H bonds DOI
Hui Cao,

Degong Kong,

Li‐Cheng Yang

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(10), P. 794 - 803

Published: Aug. 4, 2022

Language: Английский

Citations

50
Membrane-based TBADT recovery as a strategy to increase the sustainability of continuous-flow photocatalytic HAT transformations DOI Creative Commons
Zhenghui Wen, Diego Pintossi, Manuel Nuño

et al.

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

Published: Oct. 18, 2022

Photocatalytic hydrogen atom transfer (HAT) processes have been the object of numerous studies showcasing potential homogeneous photocatalyst tetrabutylammonium decatungstate (TBADT) for functionalization C(sp3)-H bonds. However, to translate these into large-scale industrial processes, careful considerations catalyst loading, cost, and removal are required. This work presents organic solvent nanofiltration (OSN) as an answer reduce TBADT consumption, increase its turnover number lower concentration in product solution, thus enabling photocatalytic HAT-based transformations. The operating parameters a suitable membrane recovery acetonitrile were optimized. Continuous alkylation amination reactions carried out with in-line via two OSN steps. Promisingly, observed yields recycling comparable those performed pristine TBADT, therefore highlighting that not only (>99%, TON > 8400) is possibility, but also it does happen at expense reaction performance.

Language: Английский

Citations

42
One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation DOI

P. Scott Pedersen,

David C. Blakemore,

Gary M. Chinigo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21189 - 21196

Published: Sept. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

Language: Английский

Citations

40
Aliphatic sulfonyl fluoride synthesis via reductive decarboxylative fluorosulfonylation of aliphatic carboxylic acid NHPI esters DOI

Zhanhu Ma,

Yongan Liu, Xiaoyu Ma

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(4), P. 1115 - 1120

Published: Jan. 1, 2022

A general and efficient approach to various aliphatic sulfonyl fluorides by the reductive decarboxylative fluorosulfonylation of carboxylic acids via a radical sulfur dioxide insertion fluorination strategy was developed.

Language: Английский

Citations

39
Photoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons DOI Creative Commons
Ping‐Fu Zhong, Jia‐Lin Tu,

Yating Zhao

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 16, 2023

Organoboron compounds are of high significance in organic synthesis due to the unique versatility boryl substituents access further modifications. The demand for incorporation moieties into molecular structures has witnessed significant progress, particularly C(sp3)-H borylation hydrocarbons. Taking advantage special characteristics photo/electrochemistry, we herein describe development an oxidative reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy. exhibits broad substrate scope (>57 examples), includes use simple alkanes, halides, silanes, ketones, esters nitriles as viable substrates. Notably, unconventional regioselectivity is achieved, with coupling site selectively located distal methyl group. Our method operationally easily scalable, offers a feasible approach one-step high-value organoboron building blocks from hydrocarbons, which would provide ample opportunities drug discovery.

Language: Английский

Citations

36