Diastereoselective synthesis of polycyclic indolinesviadearomative [4 + 2] cycloaddition of 3-nitroindoles withortho-aminophenylp-quinone methides

Zhou, Shun; Qian, Hui-Ling; Zhao, Jian‐Qiang; Wang, Zhenhua; Yin, Jin-Qing; Zhang, Yanping; Chen, Mingfeng; Yuan, Wei‐Cheng

doi:10.1039/d2ob02303b

Cited by 5 publications

(2 citation statements)

References 54 publications

(18 reference statements)

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“…On the other hand, we have noticed that in the field of para -quinone methides ( p -QMs) chemistry [ 34 , 35 , 36 , 37 ], ortho -hydrophenyl p -QMs have been used as donors to trigger some cycloaddition reactions with electron-deficient 2π-components, providing an access to chromans with structural diversity [ 38 , 39 , 40 , 41 , 42 , 43 , 44 ]. Along this line, as well as our continuing efforts on the dearomatization of nitroheteroarenes [ 45 , 46 , 47 , 48 ], we conceived that the dearomative [4 + 2] cycloaddition of electron-deficient 3-nitroindoles and ortho -hydrophenyl p -QMs might occur via the tandem oxy -Michael addition/1,6-addition under alkaline conditions ( Scheme 2 b) [ 49 ]. To our surprise, the reaction between 3-nitroindoles and ortho -hydrophenyl p -QMs did undergo smoothly but providing unanticipated N -alkylation products via protection group migration/ aza -1,6-Michael addition pathway instead of the dearomative [4 + 2] cyclo-adducts ( Scheme 2 c).…”

Section: Introductionmentioning

confidence: 99%

3-Nitroindoles Serving as N-Centered Nucleophiles for Aza-1,6-Michael Addition to para-Quinone Methides

et al. 2023

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An unprecedented N-alkylation of 3-nitroindoles with para-quinone methides was developed for the first time. Using potassium carbonate as the base, a wide range of structurally diverse N-diarylmethylindole derivatives were obtained with moderated to good yields via the protection group migration/aza-1,6-Michael addition sequences. The reaction process was also demonstrated by control experiments. Different from the previous advances where 3-nitrodoles served as electrophiles trapping by various nucleophiles, the reaction herein is featured that 3-nitrodoles is defined with latent N-centered nucleophiles to react with ortho-hydrophenyl p-QMs for construction of various N-diarylmethylindoles.

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Section: Introductionmentioning

confidence: 99%

3-Nitroindoles Serving as N-Centered Nucleophiles for Aza-1,6-Michael Addition to para-Quinone Methides

et al. 2023

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“…Despite the formation of a substantial quantity of the byproduct, viz. allylic sulfone 4 , the expected outcome, i.e., formation of the ring in the desired compound 3a via syn-addition, was observed . Despite the presence of multiple stereogenic carbon centers within the product, only a pair of enantiomers ( 3a ) was observed.…”

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confidence: 99%

Synthesis of Stereoselective Multifused Cyclic Compounds via Palladium-Catalyzed C3-Allylative Dearomatization

Im,

Jung,

Park

et al. 2023

ACS Catal.

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In this study, Pd-catalyzed enantioselective C3-allylative dearomatization is performed, which proceeds via dearomative [3 + 2] cycloaddition involving quinolinium zwitterions and vinyl cyclopropanes. This protocol is significant for the synthesis of complex, multifused cyclic compounds characterized by meticulously controlled multistereogenic centers using π-allyl palladium species. The method developed herein presents an approach to overcoming the challenge of achieving stereoselective C3functionalization. The SEGPHOS ligand plays an integral role in this process by improving both the conversion rates and stereoselectivity. Our investigation also underscores the versatility of this methodology by demonstrating its potential for the construction of stereocontrolled fused N-cyclic systems. The results of this study lay the foundation for the further exploration and refinement of asymmetric dearomatization aimed at the strategic construction of stereoselective N-heterocyclic compounds.

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Dearomative [4 + 2] cycloaddition of 3‐nitroindoles with ortho‐amino Morita−Baylis−Hillman carbonates to forge indole‐fused quinolines

Wang,

Li,

et al. 2024

Journal of Heterocyclic Chem

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A dearomative [4 + 2] cycloaddition of 3‐nitroindoles ortho‐amino Morita−Baylis−Hillman carbonates was established under mild conditions. This method provides an efficient and practical approach for delivering tetrahydro‐5H‐indolo[2,3‐b]quinolines containing three contiguous stereocenters, two tertiary and one quaternary, in high yield (up to 95%) with excellent diastereoselectivity (all cases >25:1 dr). The potential synthetic applications of this strategy were also highlighted by the scale‐up experiment and further synthetic transformation. Moreover, the structure and relative configuration of the cycloadduct was unequivocally confirmed by single‐crystal X‐ray diffraction.

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Diastereoselective synthesis of polycyclic indolinesviadearomative [4 + 2] cycloaddition of 3-nitroindoles withortho-aminophenylp-quinone methides

Abstract: A formal [4+2] cycloaddition of 3-nitroindoles with ortho-aminophenyl p-quinone methides via a dearomatization process was developed. This method provided a facile protocol for preparing tetrahydro-5H-indolo[2,3-b]quinolones in good results. With a...

Cited by 5 publications

References 54 publications

3-Nitroindoles Serving as N-Centered Nucleophiles for Aza-1,6-Michael Addition to para-Quinone Methides

3-Nitroindoles Serving as N-Centered Nucleophiles for Aza-1,6-Michael Addition to para-Quinone Methides

Synthesis of Stereoselective Multifused Cyclic Compounds via Palladium-Catalyzed C3-Allylative Dearomatization

Dearomative [4 + 2] cycloaddition of 3‐nitroindoles with ortho‐amino Morita−Baylis−Hillman carbonates to forge indole‐fused quinolines

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