Benzazetidines and Related Compounds: Synthesis and Potential

Salvio, Riccardo; Placidi, Simone; Bella, Marco

doi:10.1002/chem.201905668

Cited by 5 publications

(3 citation statements)

References 112 publications

(135 reference statements)

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“…Other alkylamines except benzylamine are not tolerated in this transformation, probably due to their strong basicity. Furthermore, the following transformation of the arylated products 57 - I using diversity-oriented synthesis strategy finally builds a chemical drug library of diverse heterocyclic fragments 57 that are in demand in the drug discovery field. − …”

Section: Synthetic Applications Of Cyclic Aryliodoniumsmentioning

confidence: 99%

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

et al. 2023

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Hypervalent aryliodoumiums are intensively investigated as arylating agents. They are excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions to be performed under mild conditions. In the past decades, acyclic aryliodoniums are widely explored as arylation agents. However, the unmet need for acyclic aryliodoniums is the improvement of their notoriously low reaction economy because the coproduced aryl iodides during the arylation are often wasted. Cyclic aryliodoniums have their intrinsic advantage in terms of reaction economy, and they have started to receive considerable attention due to their valuable synthetic applications to initiate cascade reactions, which can enable the construction of complex structures, including polycycles with potential pharmaceutical and functional properties. Here, we are summarizing the recent advances made in the research field of cyclic aryliodoniums, including the nascent design of aryliodonium species and their synthetic applications. First, the general preparation of typical diphenyl iodoniums is described, followed by the construction of heterocyclic iodoniums and monoaryl iodoniums. Then, the initiated arylations coupled with subsequent domino reactions are summarized to construct polycycles. Meanwhile, the advances in cyclic aryliodoniums for building biaryls including axial atropisomers are discussed in a systematic manner. Finally, a very recent advance of cyclic aryliodoniums employed as halogen-bonding organocatalysts is described.

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Section: Synthetic Applications Of Cyclic Aryliodoniumsmentioning

confidence: 99%

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

et al. 2023

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“…In this context, a preparative methodology to obtain benzazetidines strained an inherently unstable N-heterocycles was recently reported by our group [39,40]. This method consists in trapping a four-membered hemiaminal structure, in equilibrium with from 2-(N-Boc-anilino)-α ketoesters 15, by the use 4-dimethylaminopyridine in catalytic amounts, and affords benzazetidines in good yields.…”

Section: Catalytic Activity Measurementsmentioning

confidence: 99%

“…These compounds were selected because of their straightforward synthesis and the cheapness of the reagents used in the procedures. Their catalytic activity was tested in t-butoxycarbonyl transfer reactions such as the kinetic resolution of alcohols and the enantioselective preparation of benzazetidines [39,40] showing, in some cases, good yields and fair enantiomeric ratios.…”

Section: Introductionmentioning

confidence: 99%

Preparation of chiral DMAP derivatives and investigation on their enantioselective catalytic activity in benzazetidine synthesis and kinetic resolutions of alcohols

Placidi

D'Intignano

Salvio

2022

Journal of Heterocyclic Chem

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4‐dimethylaminopyridine (DMAP) is an extremely versatile catalyst active in a large series of chemical transformations because of its relevant basicity and nucleophilicity. In this paper, we present the synthesis of two chiral DMAP derivatives starting from 4‐halopyridine and l‐proline benzyl ester. The key steps of these preparations are a ZnII‐coordinated dimer of proline ester and a variation of the Buchwald‐Hartwig promoted by copper(I) salts. The preparation of these compounds was achieved with the use of inexpensive materials and facile procedures and does not require the use of any catalyst based on transition metals. In addition, these procedures open up the way for the preparation of a large variety of chiral DMAP organocatalysts. Their catalytic activity was tested in t‐butoxycarbonyl transfer reactions, chosen as a benchmark because these transformations potentially profit from the presence of a nucleophilic catalyst. The kinetic resolution of alcohols and the enantioselective preparation of benzazetidines, in some experiments, was achieved with a noticeable enantiomeric ratio.

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