Photoinduced Asymmetric Alkene Aminohetarylation with Chiral Sulfoximine Reagents DOI Open Access
Zhu Cao,

Sun Yu-qian,

Yasu Chen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(47)

Published: Aug. 15, 2024

Abstract Given the pivotal role of β ‐(het)arylethylamine moiety in bioactive molecules, direct amino(het)arylation alkenes occupies a privileged position construction (het)arylethylamine derivatives. Herein we devise chiral sulfoximines as novel bifunctional reagents which exhibit remarkable efficiency challenging asymmetric alkene aminohetarylation reaction, particularly terms reactivity and stereo‐control. The can be conveniently accessed gram scale, efficiently generate N ‐centered radicals under mild photochemical conditions. transformation proceeds through enantioselective 1,4‐hetaryl migration, ensuring precise chirality transfer from sulfur‐ to carbon‐centers, rendering wide applicability both aromatic aliphatic alkenes. Furthermore, method is straightforward operate does not require transition metals or photosensitizers, making it an attractive practical option.

Language: Английский

Electrochemical oxidative CF3 radical-induced lactonization and etherification of terminal and internal alkenes DOI Creative Commons

Riccardo Grigolato,

Tommaso Fantoni,

Giuseppe Autuori

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(19), P. 15302 - 15309

Published: Jan. 1, 2025

Introducing CF 3 groups boosts drug properties by enhancing metabolic stability and bioavailability. This study reports an electrochemical oxidative difunctionalization of flexible alkenes to form -substituted lactones cyclic ethers.

Language: Английский

Citations

0
Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 30, 2024

An electrochemical radical Truce Smiles rearrangement of N-allylbenzamides is documented herein. The selective 1,4-aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β-arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N-allylbenzamide crucial outcompete undesired 6-endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Citations

3
Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides DOI Creative Commons
Wei‐Yang Ma, Matteo Leone, Étienne Derat

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 18, 2024

The radical Truce-Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules which asymmetric processes remains rare. By employing readily available and non-expensive chiral auxiliary, we developed highly efficient photocatalytic acyl alkyl of α-substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as hydrogen atom-transfer photocatalyst, along with aldehydes or C-H containing precursors. rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 2 d.r.) auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in density functional theory (DFT) calculations provided insights stereochemistry-determining step.

Language: Английский

Citations

2
The merger of electro-reduction and hydrogen bonding activation for a radical Smiles rearrangement DOI Creative Commons

Liyuan Lan,

Kun Xu, Cheng‐Chu Zeng

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13459 - 13465

Published: Jan. 1, 2024

An unprecedented radical smiles rearrangement of N -arylpropiolamides was realized by merging electro-reduction with hydrogen bonding activation. Enabled this dual activation strategy, the reduction potential shifted positively 218 mV.

Language: Английский

Citations

2
Vicinal Difunctionalization of Unactivated Alkenes Through Radical Addition/Remote (Hetero)Aryl Migration Cascade DOI Creative Commons
S. Meyer, Aurélie Claraz

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(43)

Published: Sept. 9, 2024

Abstract Alkenes are ubiquitous in natural and synthetic molecules constitute versatile building blocks. Remarkably, their radical 1,2‐difunctionalization offers a valuable tool for rapidly accessing multifunctional compounds through step atom‐ economy process. More particularly, the addition of (hetero)aromatic groups onto alkenes is particular appeal given numerous applications aromatic various fields. However, such process becomes difficult when attempted on simple non‐conjugated aliphatic (unactivated alkenes). In this context, (hetero)arylation unactivated functionalization followed by remote (hetero)aryl migration has recently emerged as powerful opportunity to address lack reactivity π systems. The advances chemistry have led flood methods trigger carbon‐ or heteroatom‐centered radical/(hetero)aryl sequence. Interestingly, ring can take place from atoms. This feature spurred design several substrates allowing occur. review intends provide an overview contributions according type that been employed. reaction scope, limitations mechanistic aspect will be discussed with aim stimulating efforts research area.

Language: Английский

Citations

2
Transition Metal and Base‐Free Electro‐Oxidative Regioselective Trifluoromethylation of Imidazo[1,2‐a]pyridines DOI
Atreyee Halder, Sayan Ghosh, Suman De Sarkar

et al.

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(8)

Published: June 27, 2023

Abstract A green electrochemical C(sp 2 )−H trifluoromethylation of imidazo[1,2‐ a ]pyridines by engaging Langlois’ reagent is reported. This oxidative regioselective CF 3 ‐functionalization strategy operates under open atmosphere, in an undivided cell and at ambient temperature. Regioselective C−CF bond formation was achieved exclusively applying this mild protocol exhibiting broad functional group compatibility affording the desired product up to 79% isolated yield. Mechanistic studies indicated radical pathway for redox transformation.

Language: Английский

Citations

6
Electrochemical Synthesis of Aryl Chlorides Using HCl as the Chlorine Source DOI
Tao Shen,

Yuanbo Xu,

Chengjun Jiang

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(8), P. 3289 - 3297

Published: Feb. 13, 2024

Hydrochloric acid (HCl) is abundantly generated as the byproduct in chemical industry. The recycling of chloride from HCl related to intensive energy input and resource consumption. European Commission Joint Research Centre stated that production utilization chlorine are indicative development level To utilize a green way, an unprecedented, straightforward, simple electrosynthesis method has been employed produce chlorinated aromatics. control experiments indicated reaction underwent free radical pathway mass transfer was crucial for reaction. Further, microchannel flow electroreactor further used scale up overcome hydrophobic obstacle graphite electrode surface, hydrophilic modification with nitric used. After modification, content O element increased 1.1 2.3%, C–O–C unit 10.9 16.2%, O–C═O 27.1 28.2%. Thus, desired product afforded satisfactory yields under modified electrode.

Language: Английский

Citations

1
Electrochemical synthesis of β-difluoromethylamide compounds by N-benzenesulfonylacrylamide with difluorine reagents DOI

Zhi-Long Lei,

Zong‐Cang Ding,

Shu‐Hui Li

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(59), P. 7614 - 7617

Published: Jan. 1, 2024

A mild and efficient electrochemical method for radical addition, cyclization, migration reaction was described in this work. difluoromethyl produced by anodizing CF

Language: Английский

Citations

1
Photo-Induced Difluoroalkylation/Cyclization of Alkyne Ketones: A Novel Strategy to Access Difluoroalkyl Thiofavones DOI

Shengjie Song,

Can Luo,

Guan Wang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A photo-induced electron donor-acceptor (EDA) complex enabled tandem reaction of alkyne ketones

Language: Английский

Citations

1
Photocatalytic Asymmetric Acyl Radical Truce–Smiles Rearrangement for the Synthesis of Enantioenriched α‐Aryl Amides DOI Creative Commons
Wei‐Yang Ma, Matteo Leone, Étienne Derat

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(37)

Published: June 18, 2024

Abstract The radical Truce–Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules which asymmetric processes remains rare. By employing readily available and non‐expensive chiral auxiliary, we developed highly efficient photocatalytic acyl alkyl of α‐substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as hydrogen atom–transfer photocatalyst, along with aldehydes or C−H containing precursors. rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 2 d.r.) auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in density functional theory (DFT) calculations provided insights stereochemistry‐determining step.

Language: Английский

Citations

1