Chiral chromane[4]arenes synthesised by cycloaddition reactions of<i>o</i>-quinomethine resorcin[4]arenes

Stefańska, Karolina; Szafraniec, Anna; Szymański, Marek P.; Wierzbicki, Michał; Szumna, Agnieszka; Iwanek, Waldemar

doi:10.1039/c8nj06179c

Cited by 8 publications

(8 citation statements)

References 35 publications

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“…12 Among other things, spatially developed structures such as cavitands, [13][14][15][16] dimeric capsules, [17][18][19][20] and hexamers [21][22][23][24] can be constructed based on such skeletons, and these can be used to study the reactivity of chemical compounds in spatially limited or closed structures. [25][26][27][28] One possibility for modifying the structure of resorcin [4] arene was our use of the methoxy derivative of resorcin [4]arene for the thermal generation of the o-quinone methide derivative of resorcin [4]arene, followed by a cycloaddition reaction [29][30][31] and Michael reaction with C, Pnucleophiles. 32,33 Until now, the synthesis of cyclochiral derivatives of resorcin [4]arene was based on two approaches: (1) structural modications of the skeleton of the resorcin [4]arene molecule via covalent bonds; 4,5 (2) on the selection of appropriate substrates for the synthesis of cyclochiral resorcin [4]arene molecules.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a coumarin derivative of resorcin[4]arene with solvent-controlled chirality

Szafraniec

Iwanek

2020

RSC Adv.

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Section: Introductionmentioning

confidence: 99%

Synthesis of a coumarin derivative of resorcin[4]arene with solvent-controlled chirality

Szafraniec

Iwanek

2020

RSC Adv.

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“…In an earlier paper, 13 the possibility of synthesising 4hydroxycoumarin derivatives of resorc [4]arene was shown using the Michael reaction of the o-quinomethine derivative of resorc [4]arene, which was generated thermally from the methoxy derivative of resorc [4]arene. The resulting 4-hydroxycoumarin derivative of resorc [4]arene exhibited a variable 'in-out' conformation depending on the reaction environment.…”

Section: Resultsmentioning

confidence: 99%

New insights into the reactivity of aminomethylene derivatives of resorc[4]arene: amine group transfer, conformational analysis, reaction mechanism

Iwanek

2022

RSC Adv.

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“…Chromane [4] arenes were obtained by the Diels-Alder reaction between the o-quinone methides of resorcin [4] arene and styrenes [34]. The authors identified their compounds as chiral, but actually, they were racemic mixtures.…”

Section: Cycloaddition Of Ortho-quinone Methidesmentioning

confidence: 99%

Recent Advances in Organocatalyzed Asymmetric Synthesis of Benzopyran and Benzodihydropyran (Chromane) Nuclei

Dalpozzo

Mancuso

2019

Symmetry

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Benzopyran and benzodihydropyran (chromane) nuclei are the core structure of many natural products, in particular flavonoids. Many compounds possessing this structure are nutraceuticals, pharmaceutical nutrients. Therefore, benzopyran and chromane scaffolds are important building blocks in organic synthesis and many efforts have been made to set up efficient methods for their synthesis. In particular, asymmetric methods are of great importance, being natural products, and generally chiral substances. This review aims to cover literature in the range 2017-first half of 2019.It should be noted that the oxa-Michael-Henry reaction between two molecules of nitrostyrene was not observed. Symmetry 2020, 12, x FOR PEER REVIEW 4 of 33 Scheme 2. Heterogeneous enantioselective synthesis of chromanes.Xia, Xu and co-workers performed an enantioselective, organocatalytic oxa-Michael-nitro-Michael reaction, but in this case, too, 2-hydroxynitrostyrenes reacted only with β-nitroolefins different from themselves [10]. The reaction afforded chiral chromane derivatives bearing three contiguous stereogenic centers (Scheme 3). The all-S stereochemistry was assigned by X-ray analysis. Subsequently, Andrés, Pedrosa and co-workers extended the reaction to polymer-supported squaramides [11]. Initially, they tested some 4-vinylphenyl-substituted squaramides and found that Squa2 (see Scheme 1, 5 mol%, rt, 12-72 h in dichloromethane) gave the best results (65-88% yields, 63:27 to >99:1 dr, 70-> 99% ee, 13 examples). The absolute configuration was once more (2S,3S,4S) and was established by X-ray analysis. The configuration of the minor isomer was instead established as (2S,3R,4S) by comparison of the 1 H-NMR coupling constants of the two diastereomers. Then Squa2 was co-polymerized with styrene and divinylbenzene and the experiments were repeated (65-86% yields, 58:42 to >99:1 dr, 56-74% ee). The polymer-supported catalyst was also recovered and recycled five times without affecting yields and selectivity. Finally, the enantiomers were obtained from a squaramide derived from (1R,2R)-1,2-cyclohexanediamine instead of Squa2 derived from α-amino acid. The authors attributed the opposite stereochemistry to a different assembly of the ternary complex formed by catalyst, nitroalkene and 2-hydroxynitrostyrene in the two cases. S O HN HO HO OHC Symmetry 2019, 11, 1510 5 of 31 Symmetry 2020, 12, x FOR PEER REVIEW 5 of 33 Scheme 3. Organocatalytic oxa-Michael nitro-Michael domino reaction.Another domino Michael/hemiacetalization (see also Scheme 2, eq 3) was carried out between aliphatic aldehydes and (E)-2-(2-nitrovinyl)phenols under modularly designed organocatalysts (Scheme 4) [12]. Cis-3,4-disubstituted chroman-2-ones were obtained after oxidation of the hemiacetal intermediate or chromanes after dehydroxylation. The reaction was scaled up to 0.5 mmol scale, without significant modification of yield and selectivity. The absolute stereochemistry was determined by the optical rotation of known compounds. Scheme 4. Domino reaction catalyzed by MDO o...

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Chiral chromane[4]arenes synthesised by cycloaddition reactions ofo-quinomethine resorcin[4]arenes

Abstract: The synthesis of cavity-extended cyclochiral heterocyclic derivatives of chromane[4]arenes by a cycloaddition reaction between the o-quinomethine derivative of resorcin[4]arene and various styrenes is described.

Cited by 8 publications

References 35 publications

Synthesis of a coumarin derivative of resorcin[4]arene with solvent-controlled chirality

Synthesis of a coumarin derivative of resorcin[4]arene with solvent-controlled chirality

New insights into the reactivity of aminomethylene derivatives of resorc[4]arene: amine group transfer, conformational analysis, reaction mechanism

Recent Advances in Organocatalyzed Asymmetric Synthesis of Benzopyran and Benzodihydropyran (Chromane) Nuclei

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