Catalytic oxidation of 4-piperidone-3-carboxylates with manganese(III) acetate in the presence of 1,1-disubstituted alkenes

Kumabe, Ryoukou; Nishino, Hitoo; Yasutake, Mikio; Nguyễn, Vân Hà; Kurosawa, Kazu

doi:10.1016/s0040-4039(00)01884-0

Cited by 26 publications

(6 citation statements)

References 24 publications

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“…The reaction was then more generalized on 1,3 dicarbonyl systems with at least a ketone as function and Mn(II)(OAc)3 as a radical initiator. Piperidone 81, for example, gave rise to endoperoxide 83, 113 whereas piperidinedione 84 afforded dioxanol 86. 114 When a third carbonyl group is used as substituent, the reaction could afford tricyclic structures after a further cyclization.…”

Section: Formal [2+2+2] Cycloaddition Of Triplet Oxygen To Enoxy Radicals and Olefinsmentioning

confidence: 99%

Advances in the synthesis of 1,2-dioxolanes and 1,2-dioxanes

Ferrié

2021

Advances in Heterocyclic Chemistry

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Section: Formal [2+2+2] Cycloaddition Of Triplet Oxygen To Enoxy Radicals and Olefinsmentioning

confidence: 99%

Advances in the synthesis of 1,2-dioxolanes and 1,2-dioxanes

Ferrié

2021

Advances in Heterocyclic Chemistry

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“…For further examples and applications of related chemistry from the Nishino group (see ref. [41][42][43][44][45][46][47][48][49][50][51].…”

Section: Exploitation Of Can (Ceric Ammonium Nitrate) Promoted Singlementioning

confidence: 99%

Treasures old and new: what we can learn regarding the macrocyclic problem from past and present efforts in natural product total synthesis

et al. 2020

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“…On the other hand, these carbon signals clearly showed in those of the products bearing a substituent at the C-8 position (2m, 2n, 2p, and 2s), and N-benzoyl 2d and the N-alkoxycarbonyl-protected 2e-h. The former must be due to the flipping like a pseudo-chair form A and twist-boat form B of the dihydroquinoline skeleton within the NMR time scale (Figure 1) 15 and the latter should be assigned to the rigid scaffold. The HMQC correlations of 2a between H-2 methylene proton signals and a broad peak of the C-2 methylene carbon, and the HMBC between H-2 methylene proton peaks and a weak signal of the C-8a aromatic carbon were definitely observed (Figure 1).…”

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Mn(III)-Based Oxidative Cyclization of 2-((2-Arylamino)ethyl)malonates: Synthesis of Quinolines via Dihydroquinolinedicarboxylates

Nishino¹,

Nagashimada²,

Morikawa³

et al. 2021

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The synthesis of quinolines from aniline derivatives via the Mn(III)-based oxidative cyclization of 2-(2-(arylamino)ethyl)malonates is described. The 2-(2-(arylamino)ethyl)malonates were prepared in two steps from the substituted anilines. The cyclization of nineteen arylaminoethylmalonates protected by the N-acyl and N-alkoxycarbonyl groups easily proceeded in the formal 6-endo mode regardless of the presence of halo, methyl, and methoxy groups on the aromatic ring, and the corresponding tetrahydroquinolinedicarboxylates were produced in high yields except for the 2,4-dimethoxyphenyl-substituted aminoethylmalonate which occurred by ipso-cyclization. The tetrahydroquinolinedicarboxylate could be transformed into quinoline via decarboxylation and deprotective hydrolysis. The characteristic phenomenon in the NMR spectrum of the tetrahydroquinolinedicarboxylates is also discussed. INTRODUCTIONThe cyclization reaction is an important technique for preparing useful organic molecules, 1 in which manganese(III) acetate dihydrate, Mn(OAc) 3 •2H 2 O, is one of the best reagents especially when used in the oxidative cyclization reactions. 2 It is well-known that the Mn(III)-based oxidation of 2'-hydroxychalcones and 2-hydroxybenzophenones affords aurones 3 and 9-xanthenones 4 according to the formal 5-exo and 6-endo C-O bond cyclization. Snider, 5 Citterio, 6 and Chuang 7 reported the efficient carbon-carbon bond cyclization of 3-oxo-9-aryl-6-nonenoates, 1-aryl-7-nonene-1,3-diones, and arylalkylmalonates (Scheme 1, eq. 1), which proceeded in the similar 5-exo and 6-endo modes to give the corresponding cyclization products, such as octahydrophenanthrenes, 5a tetrehydroanthracenones, 5b,c dihydroindenes, 6a tetrahydronaphthalenes, 2a,6a dihydrobenzofurans, 5d chromanes, 8 and dihydrotetraphenediones. 7a It could also be used for the N-alkyl-N-aryl-3-oxobutanamides (eq. 2) and(2-(N-alkyl-N-arylamino)-2-oxoethyl)malonates (eq. 3), producing indolinones 9,10 and dihydroquinolinones based on the reaction. 7c,11 These compounds are important as a starting material for the synthesis of substituted indoles and quinolines, which are indispensable in natural alkaloid synthesis.Although it was easy to prepare the N-arylalkanamide starting materials, reduction of lactam carbonyl group and N-alkyl deprotection of the cyclization products need at the late stage in order to synthesize the final quinolines (eq. 3) as well as indole derivatives (eq. 2). Scheme 1. Mn(III)-Based Oxidative Radical CyclizationWe then envisioned the direct preparation of (arylamino)ethylmalonates I which would undergo the Mn(III)-based cyclization to provide the dihydroquinolines II, then easily converting into the quinolines (Scheme 2). In order to realize this enterprise, we proposed the retrosynthetic scheme from inexpensive commercially-available materials (Scheme 2). The target quinolines would be obtained by the usual decarboxylation of the 2,3-dihydroquinoline-4,4-dicarboxylates II probably produced by the key oxidation of the 2-(2-(N-arylamino)ethyl)mal...

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Catalytic oxidation of 4-piperidone-3-carboxylates with manganese(III) acetate in the presence of 1,1-disubstituted alkenes

Cited by 26 publications

References 24 publications

Advances in the synthesis of 1,2-dioxolanes and 1,2-dioxanes

Advances in the synthesis of 1,2-dioxolanes and 1,2-dioxanes

Treasures old and new: what we can learn regarding the macrocyclic problem from past and present efforts in natural product total synthesis

Mn(III)-Based Oxidative Cyclization of 2-((2-Arylamino)ethyl)malonates: Synthesis of Quinolines via Dihydroquinolinedicarboxylates

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