Gold‐Catalyzed Oxidative Alkyne Functionalization by N−O/S−O/C−O Bond Oxidants DOI
Sabyasachi Bhunia, Partha Ghosh,

Snigdha Rani Patra

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(18), P. 3664 - 3708

Published: May 11, 2020

Abstract Since the beginning of this century, homogeneous gold‐catalyzed alkyne transformations have been an active area research in pursuit developing efficient synthetic methodologies. This emerging which at exploited mild Lewis acid character gold and its propensity to form π‐complex with alkyne, has reinvigorated upon discovery oxidative functionalization 2007. The oxidation enabled direct access α‐oxo carbenes alkynal complex versatile reactivity applied achieve including but not limited oxyarylation, C−H, X−H (X=N, O) insertion, cyclization, cycloaddition, ring expansion, various cascade reactions. review provides a comprehensive summary methods, applications mechanistic insight by N−O/S−O/C−O bond oxidants covering literature reports appeared since magnified image

Language: Английский

Photochemical ring expansion reactions: synthesis of tetrahydrofuran derivatives and mechanism studies DOI Creative Commons
Sripati Jana, Zhen Yang, Chao Pei

et al.

Chemical Science, Journal Year: 2019, Volume and Issue: 10(43), P. 10129 - 10134

Published: Jan. 1, 2019

We have shown light mediated ring-expansion reactions of 4-membered ring heterocycles. The reaction proceeds via a diradical mechanism and bond length play key role in the stereodetermining step.

Language: Английский

Citations

101
Chiral Phosphoric Acid Catalyzed Enantioselective Synthesis of α-Tertiary Amino Ketones from Sulfonium Ylides DOI
Wengang Guo,

Yuzheng Luo,

Herman H. Y. Sung

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(33), P. 14384 - 14390

Published: July 22, 2020

Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones, which is particularly useful less accessible acyclic α-tertiary cases. By protonation–amination sequence, our represents rare H–heteroatom bond insertion by α-carbonyl sulfonium ylides, an attractive surrogate diazocarbonyls. The mild intermolecular C–N formation was catalyzed phosphoric acids with excellent efficiency and enantioselectivity. products are precursors to other important amine derivatives, including drug molecules ligands. enantioselectivity controlled dynamic kinetic resolution in amination step, rather than initial protonation. This process opens up platform development related reactions.

Language: Английский

Citations

94
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

93
Rhodium-Catalyzed Reaction of Sulfoxonium Ylides and Anthranils toward Indoloindolones via a (4 + 1) Annulation DOI
Xiaopeng Wu, Yan Xiao, Song Sun

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(17), P. 6653 - 6657

Published: Aug. 19, 2019

A rhodium-catalyzed annulation between aroyl sulfoxonium ylides and anthranils has been developed to synthesize 10H-indolo[1,2-a]indol-10-one derivatives. This reaction started with an unpredented (4 + 1) toward N-(2-formylphenyl) indolones, proceeding the sequential ortho-amination of C–H bond in by insertion N–H carbene. Finally, Aldol condensation constructed second indole ring. procedure features formation two C–N bonds one C═C pot.

Language: Английский

Citations

87
Photochemical, Metal‐Free Sigmatropic Rearrangement Reactions of Sulfur Ylides DOI
Zhen Yang, Yujing Guo, René M. Koenigs

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(27), P. 6703 - 6706

Published: March 28, 2019

Abstract Sigmatropic rearrangement reactions constitute one of the most fundamental carbenes. While state‐of‐the‐art synthetic methods require use expensive precious metal catalysts, application visible light for photolysis α‐aryldiazoacetates is much less investigated and provides an operationally simple entry to carbenes under mild reaction conditions. Herein, we report on blue‐light induced sigmatropic sulfur compounds with α‐aryldiazoacetates. This process, depending substitution pattern sulfide, opens up formal insertion into S−N, S−C, or C−H bonds.

Language: Английский

Citations

82
Recent application of visible-light induced radicals in C–S bond formation DOI Creative Commons
Vishal Srivastava, Pravin K. Singh, Arjita Srivastava

et al.

RSC Advances, Journal Year: 2020, Volume and Issue: 10(34), P. 20046 - 20056

Published: Jan. 1, 2020

The sulphur centered radicals, produced from various organic compounds, in high efficiency by single-electron-transfer (SET) oxidation.

Language: Английский

Citations

79
Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes DOI
Xin Liu, Li‐Gao Liu,

Can‐Ming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 14, 2023

[2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for construction C(sp3 )-S and C-C bonds. Although significant advances have been achieved, asymmetric versions via generation ylides rarely reported to date, they so far limited diazo compounds as carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse azide-ynamide cyclization, leading practical divergent assembly an array chiral [1,4]thiazino[3,2-b]indoles bearing quaternary carbon stereocenter in generally moderate excellent yields enantioselectivities. Importantly, this protocol unique catalytic non-diazo approach unprecedented [2,3]-sigmatropic α-imino carbenes.

Language: Английский

Citations

30
Ruthenium(IV) Intermediates in C−H Activation/Annulation by Weak O‐Coordination DOI
Yu‐Feng Liang, Long Yang, Torben Rogge

et al.

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(62), P. 16548 - 16552

Published: Sept. 25, 2018

Abstract Ruthenium(IV) complexes were identified as key intermediates of C−H/O−H activations by weak O ‐coordination. Thus, the annulations sulfoxonium ylides benzoic acids provided expedient access to diversely‐decorated isocoumarins with ample scope. Detailed experimental and computational studies strong support for a facile BIES‐C−H activation, along cyclometalated ruthenium(IV) within versatile ruthenium(II/IV) catalysis regime (BIES=base‐assisted internal electrophilic substitution).

Language: Английский

Citations

77
Three-Component Coupling of Aldehydes, Aminopyrazoles, and Sulfoxonium Ylides via Rhodium(III)-Catalyzed Imidoyl C–H Activation: Synthesis of Pyrazolo[1,5-a]pyrimidines DOI
Gia L. Hoang,

Andrew D. Streit,

Jonathan A. Ellman

et al.

The Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 83(24), P. 15347 - 15360

Published: Dec. 10, 2018

An efficient, three-component strategy for Rh(III)-catalyzed annulation of readily available 3-aminopyrazoles, aldehydes, and sulfoxonium ylides to give diverse pyrazolo[1,5-a]pyrimidines is disclosed. The reactions were performed under straightforward benchtop conditions using microwave heating with short reaction times. Good yields obtained many substituted aminopyrazoles a very large variety aromatic heteroaromatic including those incorporating electron-withdrawing, electron-donating, basic nitrogen, halide acidic functionality. Ester methoxy functionalities could also be directly installed on the pyrimidine ring by employing ethyl glyoxylate trimethyl orthoformate in place aldehyde, respectively. In addition, range provided products good establish that aryl, heteroaryl, branched unbranched alkyl substituents can introduced this reagent. Finally, first use formyl ylide chemical transformation enabled preparation only single substituent as aldehyde coupling partner. For ylide, one-pot, stepwise sequence was used prevent competitive condensation group aminopyrazole.

Language: Английский

Citations

70
Chemospecific Cyclizations of α‐Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls DOI Creative Commons

Daniel Clare,

Benjamin C. Dobson,

Phillip A. Inglesby

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(45), P. 16198 - 16202

Published: Sept. 11, 2019

The functionalization of aryl and heteroaryls using α-carbonyl sulfoxonium ylides without the help a directing group has remained so far neglected area, despite advantageous safety profile ylides. Described herein are cyclizations onto benzenes, benzofurans N-p-toluenesulfonyl indoles in presence base HFIP, whereas pyrroles N-methyl undergo cyclization an iridium catalyst. Significantly, these two sets conditions chemospecific for each groups substrates.

Language: Английский

Citations

68