Synthesis of chiral 4-alkyl 4-hydroxy cyclopentenones via a diastereoselective tandem aza-Cope/Mannich cyclization reaction from aldehydosugar

Kuhn, Cyrille; Gouadec, G. Le; Skaltsounis, AL; Florent, Jean‐Claude

doi:10.1016/0040-4039(95)00473-p

Cited by 26 publications

(13 citation statements)

References 30 publications

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“…This is because the cyclization leads to cyclopentyl products, with the nitrogen being lost by b-elimination, a side reaction often associated with the Mannich reaction. [98] However, this is not the only interesting aspect of this synthesis; the method of generation of the iminium ion is itself worthy of discussion. While the cationic aza-Cope rearrangement is characterized by the fact that the iminium species is already present in the molecule, the use of the aza-Claisen rearrangement offers the possibility of generating the iminium ion in the course of the reaction.…”

Section: Mannich Cyclization To Carbocyclesmentioning

confidence: 99%

Modern Variants of the Mannich Reaction

Arend

Westermann

Risch

1998

Angewandte Chemie International Edition

1,090

362

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Important building blocks for the synthesis of drugs or natural products are found in Mannich bases and their derivatives. Modern variants of the Mannich reaction that expand the potential of the classical intermolecular reaction significantly and enable efficient control of the regioselectivity and stereoselectivity are therefore the topic of intensive research. Intramolecular reactions, in particular as part of domino reaction sequences, often afford astoundingly simple and elegant approaches to complex target compounds.

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Section: Mannich Cyclization To Carbocyclesmentioning

confidence: 99%

Modern Variants of the Mannich Reaction

Arend

Westermann

Risch

1998

Angewandte Chemie International Edition

1,090

362

View full text Add to dashboard Cite

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“…The main characteristic feature of this new domino reaction resides in the unusual β‐elimination24 of the pyrrolidine nucleus occurring after the Mannich reaction. The spiro carbon atom configurations in the cyclopentenones 4 and 5 were determined with the aid of NOESY experiments and further confirmed by the RX diagram obtained from the crystalline (4 S ) major compound 4 stereoselectively prepared by the second route (vide infra) 25. We focused on demonstrating the generality of this domino cyclopentannulation with other aldehydes.…”

Section: Resultsmentioning

confidence: 81%

“…In the case of the alkylation of 21 , the minor (4 R ) isomer 23b was also isolated (< 5%). The structure of the crystalline product 22 was unambiguously determined by X‐ray analysis 25…”

Section: Resultsmentioning

confidence: 99%

Domino Aza‐Claisen/Mannich Cyclization Reaction from a Chiral α‐Alkoxy Enamine or Sequential Alkylation of an α‐Alkoxy Ester Enolate or Nitrile Anion, Followed by an Intramolecular Wittig Reaction: Two (3+2) Annulation Routes to Homochiral 4‐Alkyl‐4‐hydroxy‐2‐cyclopentenone Synthesis

et al. 2003

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A study on the enantioselective synthesis of 4-alkyl-4-hydroxyalkylidene-cyclopentenone prostaglandins is reported. Two (3+2) annulation processes allow the synthesis of homochiral 4-alkyl-4-hydroxy-2-cyclopentenones 4−5, 10−11, and 17. The first process involves a domino aza-Claisen/ Mannich cyclization reaction, resulting from the alkylation of an α-alkoxy-enamine, derived from chiral α-alkoxy aldehydes 1, 9, or 16 with 3-iodo-2-(methoxymethoxy)prop-1-ene (3) as the acetonyl equivalent. The second process is based

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“…Fe-catalyzed synthesis of α-substituted homoallylic amines. Whereas the tandem 2-aza-Cope-Mannich cyclization reaction is widely used in many natural product syntheses [71], the 3-aza-Cope-Mannich reaction homologous received scarce attention, in spite of the fact that this reaction provides 3-aminocyclopentanones [72]. Sakai's group developed a gold-catalyzed tandem 3-aza-Cope-Mannich cyclization reaction to furnish the fused N-heterocycles 158 and 158′ from cyclic tertiary alkynyl amines 157 (Scheme 33) [73].…”

Section: ]mentioning

confidence: 99%

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Lee

Kim

et al. 2022

Catalysts

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Carbon–carbon bond formation by [3,3]-sigmatropic rearrangement is a fundamental and powerful method that has been used to build organic molecules for a long time. Initially, Claisen and Cope rearrangements proceeded at high temperatures with limited scopes. By introducing catalytic systems, highly functionalized substrates have become accessible for forming complex structures under mild conditions, and asymmetric synthesis can be achieved by using chiral catalytic systems. This review describes recent breakthroughs in catalytic [3,3]-sigmatropic rearrangements since 2016. Detailed reaction mechanisms are discussed to enable an understanding of the reactivity and selectivity of the reactions. Finally, this review is inspires the development of new cascade reaction pathways employing catalytic [3,3]-sigmatropic rearrangement as related methodologies for the synthesis of complex functional molecules.

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Synthesis of chiral 4-alkyl 4-hydroxy cyclopentenones via a diastereoselective tandem aza-Cope/Mannich cyclization reaction from aldehydosugar

Cited by 26 publications

References 30 publications

Modern Variants of the Mannich Reaction

Modern Variants of the Mannich Reaction

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

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