Diastereoselective Dearomatization of Chalcone‐Based Quinolinium Salts to Assemble Bridged Quinobenzazepine Polycycles DOI Open Access

Chengxiang Luo,

Chaoyang Li, Lijie Zhang

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: unknown

Published: Sept. 13, 2023

Abstract Quinobenzazepines are useful in medicinal chemistry, but their synthesis is very challenging. Herein, we designed and synthesized a range of multi‐functional chalcone‐based quinolinium salts; synthetic application the rapid straightforward construction quinobenzazepines was successfully explored. A wide oxa‐bridged quinobenzazepine polycycles were afforded serendipitously through dearomative cascade reaction our newly developed salts acetylacetone. This strategy features high bond‐ ring‐forming efficiency complete regio‐ diastereoselective control.

Language: Английский

Recent Advances in the Dearomative Skeletal Editing of Mono-azaarenes DOI
Shengnan Jin, Qilin Wang,

Pengke Zhang

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 56(01), P. 55 - 70

Published: Jan. 17, 2023

Abstract Despite its challenges, the skeletal editing of mono-azaarenes (pyridines, quinolines, and isoquinolines) has shown unparalleled synthetic utility in construction complex molecules that are difficult to access by conventional methods. In this short review, we summarize three most recently developed strategies for deconstruction azaarene cores, with a focus on their generality, limitations, mechanistic aspects. Also, application strategy total synthesis some important natural products is discussed. 1 Introduction 2 Skeletal Editing Mono-Azaarenes through Zincke-like Reactions 3 Mono-azaarenes Aza-Buchner 4 via Photoinduced Radical or Energy-Transfer Processes 5 Conclusion

Language: Английский

Citations

20

Diastereoselective construction of bridged piperidines through an interrupted dearomative reduction DOI

Huabin Han,

Lele Wang,

Xinyue Niu

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(57), P. 7964 - 7967

Published: Jan. 1, 2022

An interrupted dearomative reduction strategy was developed to transform planar chalcone-based pyridinium salts into structurally intriguing bridged piperidines in a completely regio- and diastereoselective manner. This reaction proceeded successfully by using cheap easily accessible NaBH4 as the reductant under mild conditions without exclusion of oxygen or use special equipment.

Language: Английский

Citations

9

Substrate-directed divergent synthesis of fused indole polycycles through Rh(ii)-catalyzed cascade reactions of bis(diazo)indolin-2-ones DOI
Yang Zhao,

Xinyue Niu,

Hong Peng Yang

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(61), P. 8576 - 8579

Published: Jan. 1, 2022

Herein, we report a substrate-directed diverse synthetic strategy toward two kinds of structurally intriguing fused indole polycycles through Rh( ii )-catalyzed cascade reactions bis(diazo)indolin-2-ones with enaminones.

Language: Английский

Citations

8

Unusual N H/O H Activation Mechanism for Au-Catalyzed N,O-Functionalization of 1,4-diyn-3-ols with N-hydroxyanilines DOI Creative Commons
Yuxia Liu,

Xufang Zhao,

Jing Zhang

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 559, P. 114055 - 114055

Published: March 22, 2024

Au-catalyzed N,O-functionalization of 1,4-diyn-3-ols with N-hydroxyanilines provides a short and efficient approach to construct versatile pyrrole frameworks. Using DFT calculations, we systematically investigated the detailed mechanisms involved in this reaction. It was found that, commonly asserted NH/OH activation mechanism unfavoured due high energy barrier. The main reason believed be associated inversion configuration on sp3-hybrid C atom (generated after H(N)-shift) which results significant consumption for subsequent H(O)-shift. Therefore, here present unique "1,4-elimination/1,4-syn-protodeauration" catalytic mechanism, (i) charge delocalization carbon cation is conductive stability 1,4-elimination TS; (ii) exergonicity decreases potential surface reaction; (iii) sp2-C site ensures energy-efficient retention during 1,4-syn-protodeauration, contrast energy-consuming classical anti-protodeauration.

Language: Английский

Citations

1

Elucidating the mechanism and selectivity of [3 + 2] cycloaddition: a DFT and molecular docking investigation of the reaction of 6-butoxy-5,6-dihydro-4H-1,2-oxazine 2-oxide with dimethyl maleate DOI
Haydar Mohammad-Salim, Jesús Vicente de Julián-Ortiz,

Kholood A. Dahlous

et al.

Structural Chemistry, Journal Year: 2024, Volume and Issue: 36(1), P. 339 - 350

Published: Sept. 4, 2024

Language: Английский

Citations

1

Organophosphine as an Alkyl Transfer Shuttle for the Direct β-Alkylation of Chalcones Using Alkyl Halides DOI

Lijie Gu,

Chaoyang Li,

Xinyue Niu

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(1), P. 534 - 539

Published: Dec. 19, 2022

We report an efficient alkyl transfer strategy for the direct β-alkylation of chalcones using commercially available bromides as reagents. In this transformation, ortho-phosphanyl substituent in is crucial controlling their reactivity and selectivity. It also serves a reliable shuttle to transform electrophilic into nucleophilic species form quaternary phosphonium salts group effectively β-position chalcones. This can be further extended alkenylation benzaldehydes assemble functionalized polyenes.

Language: Английский

Citations

6

Umpolung α-regioselective 1,3-dipolar cycloaddition and internal recycle of byproduct as two key strategies: access to diverse chiral bipyridines DOI
Yu‐Heng Wang, Xirui Wang,

Ke‐Lan Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(21), P. 5428 - 5434

Published: Jan. 1, 2023

Herein, the first example of umpolung α-regioselective 1,3-dipolar cycloaddition optically pure perhydroindole-2-carboxylic acid 1a with pyridinecarboxaldehydes 2 is described.

Language: Английский

Citations

3

Solvent-controlled halohydroxylation or C3–C2 coupling of pyridinium salts through an interrupted dearomative reduction DOI
Congcong Zhang,

Qinhao Chen,

Yunlong Qin

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 60(8), P. 992 - 995

Published: Dec. 21, 2023

Herein, we report an efficient and easily operable method to halohydroxylate pyridiniums through interrupted dearomative reduction strategy. In this process, make the most of halide anion from pyridinium salts by performing reaction in DMSO without need external HX added. Notably, changing solvents into Et

Language: Английский

Citations

3

Diastereoselective dearomative bifunctionalization of isoquinolinium salts to access bridged tetrahydroisoquinolines DOI

Jiaqi Pei,

Tiantian Tang,

Jianing Zhang

et al.

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(37), P. 16151 - 16154

Published: Jan. 1, 2024

We report a diastereoselective dearomative bifunctionalization strategy of using isoquinolinium salts to access bridged tetrahydroisoquinolines through one-pot three-component cascade process.

Language: Английский

Citations

0

Mechanism of the phosphine‐catalyzed [3 + 3] annulation with MBH carbonates as the potential dipoles DOI
Tiantian Li, Zitong Chen,

Jiying Liu

et al.

Journal of Physical Organic Chemistry, Journal Year: 2022, Volume and Issue: 35(12)

Published: July 28, 2022

Abstract The [3 + 3] cylcloaddition/annulation is an important complementary for construction of six‐membered ring. With addition organophosphine to the Morita‐Baylis‐Hillman (MBH) carbonate, a potential C3 synthon can be furnished. In this work, catalytic mechanisms using as nucleophilic or electrophilic dipole react with cyclohexa‐2,5‐dienone‐substituted benzenesulfonamide are studied by density functional theory method. computational results reveal that amide anion allylic phosphonium more favorable than alkenyl in phosphorus ylide. Namely, adduct, rather ylide generated deprotonation phosphonium, likely act dipole. global reactivity index calculations indicate species involved favored pathway have better reactivities (both nucleophilicity and electrophilicity), especially significantly higher anion.

Language: Английский

Citations

2