Chiral arylsulfinylamides as reagents for visible light-mediated asymmetric alkene aminoarylations DOI Creative Commons
Cédric Hervieu, Mariia S. Kirillova, Yawen Hu

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 607 - 614

Published: Jan. 16, 2024

Abstract Two- or one-electron-mediated difunctionalizations of internal alkenes represent straightforward approaches to assemble molecular complexity by the simultaneous formation two contiguous C sp 3 stereocentres. Although racemic versions have been extensively explored, asymmetric variants, especially those involving open-shell C-centred radical species, are much more limited both in number and scope. Here we describe enantioenriched arylsulfinylamides as all-in-one reagents for efficient asymmetric, intermolecular aminoarylation alkenes. Under mild photoredox conditions, nitrogen addition arylsulfinylamide onto double bond, followed 1,4-translocation aromatic ring, produce, a single operation, corresponding adducts enantiomerically enriched form. The sulfinyl group acts here traceless chiral auxiliary, it is eliminated situ under reaction conditions. Optically pure β,β-diarylethylamines, aryl-α,β-ethylenediamines α-aryl-β-aminoalcohols, prominent motifs pharmaceuticals, bioactive natural products ligands transition metals, thereby accessible with excellent levels regio-, relative absolute stereocontrol.

Language: Английский

Illuminating Photoredox Catalysis DOI Open Access
Rory C. McAtee, Edward J. McClain, Corey R. J. Stephenson

et al.

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(1), P. 111 - 125

Published: Feb. 23, 2019

Language: Английский

Citations

436
Intermolecular radical carboamination of alkenes DOI Creative Commons
Heng Jiang, Armido Studer

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(6), P. 1790 - 1811

Published: Jan. 1, 2020

Vicinal alkene carboamination is a highly efficient and practical synthetic strategy for the straightforward preparation of diverse valuable amine derivatives starting from simple compounds. During last decade that approach has found continuous research interests various methods have been developed using transition-metal catalysis. Driven by renaissance radical chemistry, intermolecular comprising C-C bond C-N forming step intensively investigated recently culminating in novel strategies improved protocols which complement existing methodologies. Radical can be achieved via three different reaction modes. Such cascades proceed through N-radical addition to an with subsequent formation leading 2,1-carboamination products. Alternatively, installed prior initial C-radical β-amination resulting 1,2-carboamination. The third mode comprises single electron oxidation corresponding cation gets trapped N-nucleophile cascade terminated formation. In this review, conceptual approaches will discussed examples recent literature presented. Further, reader get insights into mechanism transformations.

Language: Английский

Citations

371
Radical-Mediated Remote Functional Group Migration DOI
Xinxin Wu, Chen Zhu

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(8), P. 1620 - 1636

Published: July 24, 2020

ConspectusAlkenes are ubiquitous in natural products and extensively used as synthetic feedstocks multiple fields including organic synthesis, medicinal chemistry, materials science. Radical-mediated difunctionalization of alkenes provides a powerful tactic for alkene utilization. Despite the considerable progress made past several decades, state-of-the-art methods highly dependent upon activated which proximal group with π-electron system (e.g., aryl, carbonyl, heteroatom) is requisite to stabilize nascent alkyl radical intermediate via p−π conjugation or p orbitals heteroatom. In contrast, transformation unactivated alkenes, such aliphatic remains challenging.To overcome this obstacle, we have recently disclosed strategy intramolecular distal functional migration (FGM), has been efficiently applied alkenes. A portfolio groups, cyano, heteroaryl, oximino, formyl, alkynyl showcase excellent migratory aptitude. Mechanistically, after addition an extrinsic alkene, newly formed active rapidly captured by generate cyclic intermediate. Subsequent cleavage C–C bond leads functionalized product through FGM process. Based on FGM, set elusive difunctionalizations accomplished (Part A).Alongside research, upgraded efficient strategy, "dock-migration," created intermolecular diversity sulfone-based dual-function reagents developed. The initiated docking reagent followed group. Compared original protocol, scope significantly extended from strategically placed tertiary alcohol-substituted general Both well tolerated. By approach, radical-mediated fluoroalkylheteroarylation, fluoroalkylalkynylation, alkylation achieved B).Direct elaboration C–H bonds into targeted groups represents one most ideal straightforward molecular functionalization. proves be ingenious tool functionalization remote C(sp3)–H bonds. process, accomplished: (a) heteroarylation cyanation unprotected alcohols cascade alkoxy radical-enabled hydrogen atom transfer (HAT) cyano) migration, (b) vinylation propargylic consecutive alkenyl radical-promoted HAT process subsequent C).

Language: Английский

Citations

286
Visible-Light-Driven Reductive Carboarylation of Styrenes with CO2 and Aryl Halides DOI
Hao Wang, Yuzhen Gao,

Chunlin Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

Citations

234
Radical-mediated rearrangements: past, present, and future DOI
Xinxin Wu, Zhigang Ma, Tingting Feng

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(20), P. 11577 - 11613

Published: Jan. 1, 2021

This Review summarizes the past to present achievements in radical-mediated rearrangements, and brings up prospects that may inspire colleagues develop more useful synthetic tools based on radical rearrangements.

Language: Английский

Citations

220
Visible-Light-Mediated Regioselective Chlorosulfonylation of Alkenes and Alkynes: Introducing the Cu(II) Complex [Cu(dap)Cl2] to Photochemical ATRA Reactions DOI
Asik Hossain, Sebastian Engl, Eugen Lutsker

et al.

ACS Catalysis, Journal Year: 2018, Volume and Issue: 9(2), P. 1103 - 1109

Published: Dec. 21, 2018

A visible-light-mediated photocatalyzed protocol utilizing copper–phenanthroline-based catalysts has been developed that can convert a large number of olefins into their chlorosulfonylated products. Besides the Cu(I) complex [Cu(dap)2]Cl, now well-established in photo-ATRA processes, corresponding Cu(II) [Cu(dap)Cl2] proved to be often even more efficient title reaction, being advantageous from an economic point view but also opening up new avenues for photoredox catalysis. Moreover, copper complexes outperformed commonly used ruthenium, iridium, or organic dye based photocatalysts, owing ability stabilize interact with transient radicals by inner sphere mechanisms. The use stoichiometric Na2CO3 combination photocatalysts was found essential unactivated desired products, contrast activated which no additive required. As suggested appropriate control experiments, role is attributed prevention poisoning catalyst.

Language: Английский

Citations

194
Bifunctional reagents in organic synthesis DOI
Huan‐Ming Huang, Peter Bellotti, Jiajia Ma

et al.

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(5), P. 301 - 321

Published: April 12, 2021

Language: Английский

Citations

189
Desulfonylation via Radical Process: Recent Developments in Organic Synthesis DOI
Xue‐Qiang Chu, Danhua Ge,

Yan-Ying Cui

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(20), P. 12548 - 12680

Published: Aug. 13, 2021

As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for efficient construction diverse molecular architectures by taking advantage incredible reactive flexibility. Currently, involvement in radical transformations, which sulfonyl group typically acts as a leaving via selective C–S, N–S, O–S, S–S, Se–S bond cleavage/functionalization, has facilitated new formation strategies are complementary to classical two-electron cross-couplings organometallic or ionic intermediates. Considering great influence synthetic potential these novel avenues, we summarize recent advances this rapidly expanding area discussing reaction designs, substrate scopes, mechanistic studies, limitations, outlining state-of-the-art processes involved radical-mediated desulfonylation related transformations. With specific emphasis on applications, believe review will be useful medicinal organic chemists who interested chemistry particular.

Language: Английский

Citations

184
Visible light induced alkene aminopyridylation using N-aminopyridinium salts as bifunctional reagents DOI Creative Commons
Yonghoon Moon, Bohyun Park, In‐Won Kim

et al.

Nature Communications, Journal Year: 2019, Volume and Issue: 10(1)

Published: Sept. 11, 2019

Abstract The development of intermolecular alkene aminopyridylation has great potential for quickly increasing molecular complexity with two valuable groups. Here we report a strategy the photocatalytic alkenes using variety N-aminopyridinium salts as both aminating and pyridylating reagents. Using Eosin Y photocatalyst, amino pyridyl groups are simultaneously incorporated into alkenes, affording synthetically useful aminoethyl pyridine derivatives under mild reaction conditions. Remarkably, C4-regioselectivity in radical trapping salt can be controlled by electrostatic interaction between pyridinium nitrogen sulfonyl group β-amino radical. This transformation is characterized broad substrate scope, good functional compatibility, utility this was further demonstrated late-stage functionalization complex biorelevant molecules. Combining experiments DFT calculations on mechanism investigated to propose complete regioselectivity.

Language: Английский

Citations

180
Catalytic radical generation of π-allylpalladium complexes DOI
Huan‐Ming Huang, Maximilian Koy, Eloísa Serrano

et al.

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(4), P. 393 - 400

Published: March 23, 2020

Language: Английский

Citations

179