Rh(III)-Catalyzed Coupling of <i>N</i>-Chloroimines with α-Diazo-α-phosphonoacetates for the Synthesis of 2<i>H</i>-Isoindoles

Qi, Bing; Li, Lei; Wang, Qi; Zhang, Wenjing; Fang, Lili; Zhu, Jin

doi:10.1021/acs.orglett.9b02501

Cited by 18 publications

(8 citation statements)

References 37 publications

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“…They have pointed out that indole (analogue of A-1 ) is stable while isoindole and indolizine (analogues of A-2 and A-4 , respectively) are unstable on the basis of several calculations on aromaticity, as corroborated by the fact that isoindole was synthesized 80 years later than indole . In these respects, A- m molecules except for A-1 are predicted not to be synthesized easily, but recent developments for the synthetic root of sp 2 -hybritized aza compounds including isoindole , are expected to pave a way for the synthesis of the promising A- m molecules.…”

Section: Results and Discussionmentioning

confidence: 99%

Theoretical Study on Singlet Fission in Aromatic Diaza s-Indacene Dimers

et al. 2021

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We theoretically show that diaza (N2)-substitution to s-indacene with 4n π-electrons, by which the number of π-electrons in N2-s-indacene amounts to 4n+2, is a new strategy to design efficient singlet fission (SF) molecules. By N2-substitution, the diradical character and the exchange integral are found to be tuned moderately, leading to satisfying the excitation energy level matching condition for SF with a large triplet excitation energy. On the basis of the effective electronic coupling related to the SF rate, we explore the optimal slip-stack dimer packings for fast SF. Their underlying mechanisms are well understood from the odd-electron density, resonance structure, and frontier orbital distribution, as the functions of the N2-substituted positions. Furthermore, aromaticities of N2-s-indacenes are evaluated explicitly on the basis of the magnetically induced current. Although N2-s-indacenes display strengths of aromaticities similar to that of anthracene, a local decrease in aromaticity is found to correlate to the spatial feature of diradical character, i.e., odd-electron density. The present findings not only newly propose N2-s-indacenes as feasible SF molecules but also contribute to comprehending the interplay between aromaticity and diradical electronic structures contributing to SF.

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Section: Results and Discussionmentioning

confidence: 99%

Theoretical Study on Singlet Fission in Aromatic Diaza s-Indacene Dimers

et al. 2021

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“…Because of high coordinating and oxidizing reactivity N ‐chloroimine synthon will find wide applications in transition‐metal‐catalyzed C–H functionalization. [ 34 ] Herein, we presented some metal‐catalyzed, metal‐free, and photocatalytic C–H chlorination reactions with N–Cl compounds serve this purpose.…”

Section: Oxidative Transformations (C–cl and C–o)mentioning

confidence: 99%

“…Zhu et al [ 34 ] reported the utility of N ‐chloroimines as effective substrates for C–H functionalization for the synthesis of 2H‐isoindoles (Scheme 63) Herein 2H‐isoindoles are synthesized by the coupling of N ‐chloroimines with α‐diazo‐α‐phosphonoacetates in the presence of Rh(III) catalyst, and the reaction proceeds via de‐esterification. The structural variation with the exposure of C3 and N2 ring atoms is illustrated by the ability to achieve electrophilic substitution and nucleophilic reaction, respectively.…”

Section: Application Of N‐cloroimines For the Racemization Of 1‐phenylethylamine And Preparation Of Isoquinolines And 2‐h Isoindolesmentioning

confidence: 99%

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

Govada

Reddy

2022

Applied Organom Chemis

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Owing to their various modes of coordinating and oxidizing reactivity, organic chloramines represent versatile building blocks for the synthesis of an ample range of multiatomic organic compounds. The present review focuses on synthetic methodologies using their dichotomous nature, which is the basis of their reactivity as oxidant and substrate. This is the first ever review covering the extensive applications of this large class of N–Cl compounds (organic chloramines) especially using one‐pot reaction strategies for various organic transformations, and construction of bonds such as chlorination (C–Cl, S–Cl), oxidation (C=O), cross‐coupling (C–N, CONR, S–N), cyclization, substitution, rearrangement, and catalysis, have been described, briefly to highlight important aspects of the organic chloramines in organic synthesis.

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“…In 2019, Qi et al reported a Rh(III)-catalyzed coupling of N-chloroimines 76 with -diazo--phosphonoacetates 77 that provided dechlorinative/dephosphonative access to 2H-isoindoles 78 (Scheme 18). 66 This was the first reported use of N-chloroimines for directed C-H functionalization. To generate a cationic Rh(III) catalyst, AgBF 4 was used as a halide-abstraction reagent.…”

Section: Rhodium-catalyzed Synthesismentioning

confidence: 99%

Recent Developments in Isoindole Chemistry

Wang¹,

Weintraub²

2022

Synthesis

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Isoindoles are highly reactive aromatic heterocycles that have a variety of important applications in areas such as medicine, analytical detection, and solar energy. Due to their highly reactive nature, isoindoles can be used to access their derivatives, which possess a diverse array of biological activities. However, their reactivity also makes isoindoles unstable and thus, difficult to prepare. Consequently, there has been a need for the development of novel methods that address some of the synthetic challenges and limitations, as well as reactions that utilize isoindoles to access potentially useful compounds. This review will give an overview of the novel reactions reported within the past decade (2012 to 2022) that involve 2H- and 1H-isoindoles and fused isoindoles as reactants, key intermediates, or products. This review is divided into two parts, with the first part focusing on the synthesis of isoindoles and the second part focusing on reactions of isoindoles. The scopes and limitations of the methods described therein will be discussed and the significance of their contributions to the literature will be highlighted. Similar reactions will also be compared.1 Introduction2 Synthesis of Isoindoles2.1 Synthesis of 2H-Isoindoles2.2 Synthesis of 1H-Isoindoles3 Reactions of Isoindoles3.1 Reactions of 2H-Isoindoles3.2 Reactions of 1H-Isoindoles4 Conclusions

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Rh(III)-Catalyzed Coupling of N-Chloroimines with α-Diazo-α-phosphonoacetates for the Synthesis of 2H-Isoindoles

Cited by 18 publications

References 37 publications

Theoretical Study on Singlet Fission in Aromatic Diaza s-Indacene Dimers

Theoretical Study on Singlet Fission in Aromatic Diaza s-Indacene Dimers

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

Recent Developments in Isoindole Chemistry

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