Catalytic asymmetric synthesis of α-tertiary aminoketones from sulfoxonium ylides bearing two aryl groups DOI
Ying Zhou,

Xin Yue,

Feng Jiang

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 59(9), P. 1193 - 1196

Published: Dec. 31, 2022

Disclosed herein is an efficient organocatalytic formal N-H insertion reaction of arylamines with α-keto sulfoxonium ylides bearing two aryl groups, delivering a broad range α-tertiary aminoketones good to excellent yields and enantioselectivities (up 90% yield 94% ee). The utilities this protocol were also demonstrated by facile preparation enantioenriched 2-amino-1,2-diarylethanol different type important building block lacking access.

Language: Английский

Asymmetric transformations from sulfoxonium ylides DOI Creative Commons
Clarice A. D. Caiuby, Lucas G. Furniel, Antonio C. B. Burtoloso

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 13(5), P. 1192 - 1209

Published: Dec. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Language: Английский

Citations

94
Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water DOI
Dongmei Yan,

Shuang-Hua Xu,

Hao Qian

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3279 - 3285

Published: Feb. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Language: Английский

Citations

49
Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture DOI Creative Commons
Wengang Guo, Ying Zhou,

Hongling Xie

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 14(4), P. 843 - 848

Published: Nov. 29, 2022

While asymmetric insertion of metal carbenes into H-X (X = C, N, O, etc.) bonds has been well-established, control over free is challenging due to the presence strong background reactions and lack any anchor for a catalyst interaction. Here we have achieved first photo-induced metal-free bond this type. With visible light used as promoter chiral phosphoric acid catalyst, α-diazoesters aryl amines underwent smooth N-H form enantioenriched α-aminoesters with high efficiency good enantioselectivity under mild conditions. Key success was use DMSO an additive, which served rapidly capture highly reactive carbene intermediate domesticated sulfoxonium ylide.

Language: Английский

Citations

39
Enantioselective nickel-catalysed electrochemical cross-dehydrogenative amination DOI
Kang Liang, Qinglin Zhang, Chang Guo

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(12), P. 1184 - 1193

Published: July 31, 2023

Language: Английский

Citations

34
Visible-Light-Mediated Photoredox Carbon Radical Formation from Aqueous Sulfoxonium Ylides DOI

Ning Xian,

Jiang Yin,

Xiaochen Ji

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(7), P. 1161 - 1165

Published: Feb. 9, 2023

The visible-light-induced photoredox carbon radical formation from aqueous sulfoxonium ylides has been demonstrated for the first time. While direct reduction of by H2O efficiently generates corresponding hydrocarbon compounds, use additional alkenes as acceptors alters chemical reactivity to achieve alkene carboarylation N-arylacrylamides. Mechanistic studies reveal two different reaction pathways involved in resulting release dimethyl sulfone and form DMSO.

Language: Английский

Citations

31
Highly efficient construction of 2,3-disubstituted indoline derivatives by [4 + 1] annulation of sulfur ylides and o-sulfonamido aldimines DOI
Mengjiao Xu,

Mengwei You,

Su Yang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(6), P. 1521 - 1526

Published: Jan. 1, 2023

A highly efficient [4 + 1] annulation of sulfur ylide salts and o -sulfonamido aldimines for construction valuable 2,3-disubstituted indolines is reported. It worth noting that indoles could also be synthesized by this cascade reaction.

Language: Английский

Citations

27
Chameleonic Reactivity of Imidoyl Sulfoxonium Ylides: Access to Functionalized Pyrroles and Dihydro-pyridines DOI
Jingnan Xu,

Ren‐Yin Yang,

Bo Xu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 62 - 67

Published: Jan. 3, 2024

We have found a chameleonic reactivity of imidoyl sulfoxonium ylides. On the one hand, ylides react with electron-deficient reagents, such as alkynyl esters, to lead formation 1,2-dihydro-pyridines. The methyl group attached sulfur atom acts methylene donor. other pyridinium 1,4-zwitterionic thiolates, which leads functionalized pyrroles. Both transformations feature mild reaction conditions and good functional tolerance.

Language: Английский

Citations

9
Bridging the information gap in organic chemical reactions DOI
Malte L. Schrader, Felix Schäfer,

Felix Schäfers

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 491 - 498

Published: March 28, 2024

Language: Английский

Citations

9
Catalytic Enantioselective Nucleophilic α-Chlorination of Ketones with NaCl DOI
Zhiyang Li,

Baocheng Wang,

Chaoshen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2779 - 2788

Published: Jan. 18, 2024

Catalytic enantioselective α-chlorination of ketones is a highly desirable process. Different from the conventional approaches that employ corrosive electrophilic chlorination reagents, process disclosed here employs nucleophilic chloride, aqueous NaCl solution, and even seawater, as green inexpensive chlorine sources. This mechanistically distinct electronically opposite approach provides facile access to diverse enantioenriched acyclic α-chloro are less straightforward by approaches. With chiral thiourea catalyst, range racemic α-keto sulfonium salts underwent enantioconvergent carbon–chlorine bond formation with high efficiency excellent enantioselectivity under mild conditions. The motif plays crucial triple role permitting smooth dynamic kinetic resolution take place via anion binding mechanism in well-designed phase-transfer system. protocol represents new general platform for asymmetric α-functionalization carbonyl compounds.

Language: Английский

Citations

8
Enantioselective organocatalytic strategies to access noncanonical α-amino acids DOI Creative Commons
Pietro Pecchini, Mariafrancesca Fochi, Francesca Bartoccini

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 5832 - 5868

Published: Jan. 1, 2024

Organocatalytic asymmetric synthesis has evolved over the years and continues to attract interest of many researchers worldwide. Enantiopure noncanonical amino acids (ncAAs) are valuable building blocks in organic synthesis, medicinal chemistry, chemical biology. They employed elaboration peptides proteins with enhanced activities and/or improved properties compared their natural counterparts, as chiral catalysts, ligand design, for syntheses complex molecules, including products. The linkage ncAA enantioselective organocatalysis, subject this perspective, tries imitate biosynthetic process. Herein, we present contemporary earlier developments field organocatalytic activation simple feedstock materials, providing potential ncAAs diverse side chains, unique three-dimensional structures, a high degree functionality. These strategies, useful forging wide range C-C, C-H, C-N bonds combinations thereof, vary from classical name reactions, such Ugi, Strecker, Mannich most advanced concepts deracemisation, transamination, carbene N-H insertion. Concurrently, some interesting mechanistic studies/models, information on chirality transfer Finally, perspective highlights, through diversity (AAs) not selected by nature protein incorporation, generic modes activation, induction, reactivity commonly used, enamine, hydrogen bonding, Brønsted acids/bases, phase-transfer reflecting increasingly important role applied chemistry.

Language: Английский

Citations

7