Bench-Stable Meisenheimer Complexes: Synthesis, Characterization, and Divergent Reactivity for Dearomatization DOI
Wei‐Long Zeng, Qi‐Dong Xia, Chuqiao Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30764 - 30770

Published: Oct. 30, 2024

The chemistry of the Meisenheimer complexes is fundamental interest in organic chemistry. While nitro group has been extensively employed to facilitate formation and stabilization complexes, analogous application more user-friendly ester groups remained an unexplored frontier. Herein, we report ester-stabilized which have remarkable air-, moisture-, thermo-stability. Moreover, isolable well-defined intermediates exhibit divergent reactivity for dearomatization reactions, including modular 1,4-additions, dearomative (2 + 3) cycloadditions, even higher-order (4

Language: Английский

Copper‐Catalyzed Dearomative 1,2‐Hydroamination DOI Creative Commons
Christopher William Davis, Yu Zhang, Yanrong Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 23, 2024

Catalytic olefin hydroamination reactions are some of the most atom-economical transformations that bridge readily available starting materials-olefins and high-value-added amines. Despite significant advances in this field over last two decades, formal nonactivated aromatic compounds remains an unsolved challenge. Herein, we report extension to π-systems by using arenophile-mediated dearomatization Cu-catalysis perform 1,2-hydroamination on arenes. This strategy was applied a variety substituted arenes heteroarenes provide general access structurally complex We conducted DFT calculations inform mechanistic understanding rationalize unexpected selectivity trends. Furthermore, developed practical, scalable desymmetrization deliver enantioenriched dearomatized products enable downstream synthetic applications. ultimately used dearomative efficiently synthesize collection densely functionalized small molecules.

Language: Английский

Citations

6
Umpolung‐Enabled Divergent Dearomative Carbonylations DOI
Ming‐Yang Wang, Wei‐Long Zeng,

Lin Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π-bonds through umpolung chromium-arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3- 1,4-cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

Citations

4
Photo‐Promoted Nitrogen‐Centered Radical Mediated Intermolecular Aminative Carbonylation of Tertiary Allyl Alcohols to Access β‐Amino Ketones through (Hetero)Aryl Migration DOI Creative Commons

Ming Hou,

Yuanrui Wang,

Hefei Yang

et al.

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Carbon monoxide, as a crucial C1 synthon, has been widely used in the difunctionalization of alkenes. Additionally, nitrogen‐centered radicals (NCRs) are also effective intermediates for constructing C−N bonds. Herein, radical‐mediated aminative carbonylation strategy producing β ‐amino ketones from tertiary allyl alcohols disclosed. Good yields with different functional groups were generated effectively under light irradiation.

Language: Английский

Citations

0
Chromium-Promoted Dearomative (Deutero)Hydrocyanoalkylation of (Hetero)Arenes Using Simple Alkylnitriles DOI
Wei Li, Wei‐Long Zeng,

Xu Jiang

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(10), P. 1101 - 1106

Published: Oct. 2, 2023

Abstract Herein, a general strategy for the regioselective dearomative 1,2-hydrocyanoalkylation of chromium-bound (hetero)arenes with simple alkylnitriles as pronucleophiles was disclosed, providing rapid access to 1,3-cyclohexadienes possessing useful alkylnitrile groups. The versatility this methodology further enabled selective deuteration reaction. Finally, synthetic applications method in formal synthesis natural products, including erysotramidine, demethoxyerythratidinone, and morphine, were demonstrated.

Language: Английский

Citations

4
Tungsten-anisole complex provides 3,6-substituted cyclohexenes for highly diversified chemical libraries DOI Creative Commons
Justin T. Weatherford-Pratt, Jeremy M. Bloch, Jacob A. Smith

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(7)

Published: Feb. 16, 2024

Medicinal chemists use vast combinatorial molecular libraries to develop leads for new pharmaceuticals. The syntheses of these compounds typically rely on coupling fragments through atoms with planar (sp 2 ) geometry. These so-called flat molecules often lack the protein binding site specificity needed be an effective drug. Here, we demonstrate a strategy in which cyclohexene is used as linker connect two diverse while forming tetrahedral 3 stereocenters. connections are made aid tungsten complex that activates anisole toward unusual double protonation, followed by sequential nucleophilic additions. As result, either cis- or trans-disubstituted cyclohexenes can prepared range chemical diversity unparalleled other dearomatization methods.

Language: Английский

Citations

1
Copper‐Catalyzed Dearomative 1,2‐Hydroamination DOI Creative Commons
Christopher William Davis, Yu Zhang, Yanrong Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 23, 2024

Abstract Catalytic olefin hydroamination reactions are some of the most atom‐economical transformations that bridge readily available starting materials–olefins and high‐value‐added amines. Despite significant advances in this field over last two decades, formal nonactivated aromatic compounds remains an unsolved challenge. Herein, we report extension to π‐systems by using arenophile‐mediated dearomatization Cu‐catalysis perform 1,2‐hydroamination on arenes. This strategy was applied a variety substituted arenes heteroarenes provide general access structurally complex We conducted DFT calculations inform mechanistic understanding rationalize unexpected selectivity trends. Furthermore, developed practical, scalable desymmetrization deliver enantioenriched dearomatized products enable downstream synthetic applications. ultimately used dearomative efficiently synthesize collection densely functionalized small molecules.

Language: Английский

Citations

0
Umpolung‐Enabled Divergent Dearomative Carbonylations DOI
Ming‐Yang Wang, Wei‐Long Zeng,

Lin Chen

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Abstract Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three‐dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π‐bonds through umpolung chromium–arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO‐gas‐free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3‐ 1,4‐cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late‐stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

Citations

0
Dearomative 1,2‐(Deutero)Hydrotrifluoromethylation of Chromium‐Bound Arenes DOI

Cheng‐Jie Wu,

Jiang Xu, Jia‐Yi Qiu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(20), P. 4199 - 4204

Published: July 19, 2024

Abstract Dearomative trifluoromethylation of arenes provides an ideal method for constructing CF 3 ‐containing three‐dimensional architectures which are increasing interest in drug discovery. However, such transformation is rare and challenging because the inherently low reactivity arene π‐systems selectivity issues. Herein, we disclose a general dearomative 1,2‐hydrotrifluoromethylation (hetero)arenes utilizing activation by temporary π‐complexation to chromium, thus affording convenient access 1,3‐cyclohexadienes bearing privileged group. The versatility this strategy further enables 1,2‐deuterotrifluoromethylation with high deuterated ratios. related 1,2‐(deutero)hydroperfluoroethylation reactions were conducted well range chromium‐bound (hetero)arenes. Finally, reasonable mechanism was proposed based on intermediate capture control experiments.

Language: Английский

Citations

0
Chromium‐Mediated Dearomative Allylic Addition to Arenes DOI
Wei‐Long Zeng,

Yu‐Fei Yuan,

Ming‐Yang Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(46)

Published: Aug. 23, 2024

Abstract In comparison with the well‐established allylic additions to C=O, C=N, and C=C double bonds, dearomative addition arene π‐systems is heavily underdeveloped due severe challenge in breaking aromatic resonance stabilization. Herein, we disclose a general efficient chromium‐bound arenes using allylsilanes as pronucleophiles, thus affording convenient access allyl‐functionalized 1,3‐cyclohexadiene building blocks. With commercially available deuterium sources, versatility of this strategy further enables an 1,2‐deuteroallylation high level incorporation. Finally, preliminary try on asymmetric hydroallylation based chiral auxiliary described.

Language: Английский

Citations

0
Bench-Stable Meisenheimer Complexes: Synthesis, Characterization, and Divergent Reactivity for Dearomatization DOI
Wei‐Long Zeng, Qi‐Dong Xia, Chuqiao Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30764 - 30770

Published: Oct. 30, 2024

The chemistry of the Meisenheimer complexes is fundamental interest in organic chemistry. While nitro group has been extensively employed to facilitate formation and stabilization complexes, analogous application more user-friendly ester groups remained an unexplored frontier. Herein, we report ester-stabilized which have remarkable air-, moisture-, thermo-stability. Moreover, isolable well-defined intermediates exhibit divergent reactivity for dearomatization reactions, including modular 1,4-additions, dearomative (2 + 3) cycloadditions, even higher-order (4

Language: Английский

Citations

0