Stereodivergent Synthesis of Substituted N,O‐Containing Bicyclic Compounds by Sequential Addition of Nucleophiles to <i>N</i>‐Alkoxybicyclolactams

Vincent, Guillaume; Guillot, Régis; Kouklovsky, Cyrille

doi:10.1002/anie.201006590

Cited by 90 publications

(11 citation statements)

References 71 publications

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“…Indirect methods require a preactivation step, which is a transformation of the amide functionality into a more reactive species, for example, an acylamide (DeNinno,3a Suh)3c or thioamide (Murai) 3d. e Direct methods, without the preactivation step, proved possible by using tert ‐formamides (de Meijere,3f Bélanger),3i tert ‐amides (Huang),3g, h, m–o sec ‐amides (Huang),3k and N‐alkoxyamides (Kibayashi,4f Sato and Chida,4a, b Vincent and Kouklovsky,4c, d Helmchen) 4e. However, the chemoselective version of the reaction has remained a formidable challenge because of the use of reactive organometallic reagents such as Grignard reagents and organolithium reagents prohibits functional‐group compatibility with sensitive functional groups 7.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Reductive Nucleophilic Addition to Tertiary Amides, Secondary Amides, and N‐Methoxyamides

Nakajima

Oda

Wada

et al. 2014

Chemistry A European J

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As the complexity of targeted molecules increases in modern organic synthesis, chemoselectivity is recognized as an important factor in the development of new methodologies. Chemoselective nucleophilic addition to amide carbonyl centers is a challenge because classical methods require harsh reaction conditions to overcome the poor electrophilicity of the amide carbonyl group. We have successfully developed a reductive nucleophilic addition of mild nucleophiles to tertiary amides, secondary amides, and N-methoxyamides that uses the Schwartz reagent [Cp2 ZrHCl]. The reaction took place in a highly chemoselective fashion in the presence of a variety of sensitive functional groups, such as methyl esters, which conventionally require protection prior to nucleophilic addition. The reaction will be applicable to the concise synthesis of complex natural alkaloids from readily available amide groups.

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Section: Introductionmentioning

confidence: 99%

Chemoselective Reductive Nucleophilic Addition to Tertiary Amides, Secondary Amides, and N‐Methoxyamides

Nakajima

Oda

Wada

et al. 2014

Chemistry A European J

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“…While our work was in progress, Kouklovsky, Vincent et al. published further work with bicyclic N‐ alkoxylactams, generated by a cycloaddition approach with nitroso compounds that differed from those used by the Kibayashi group 5. Finally, Chida, Sato et al.…”

Section: Introductionmentioning

confidence: 88%

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

Jäkel

Schnitzer

et al. 2013

Chemistry A European J

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Enantioselective iridium-catalyzed allylic substitutions were used to prepare N-allyl hydroxamic acid derivatives that were suitable for ring-closing metathesis, giving N-methoxylactams. Reactions of these derivatives with Grignard or organolithium compounds gave hemiaminals, which could be reduced diastereoselectively via acyliminium intermediates to give cis-piperidines or cis-pyrrolidines with substituents in the 2,6- or 2,5-positions, respectively. In addition, compounds with a quaternary carbon center could be synthesized by corresponding reactions with potassium cyanide/AcOH. The procedures were applied in the syntheses of alkaloids (-)-209D and (+)-prosophylline.

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“…This strategy was applied to the total synthesis of the alkaloid andrachcinidine, a natural product extracted from Andrachne aspera. [17] Cycloaddition between the in situ prepared N-acyl nitroso 25 and cyclopentadiene gave the cycloadduct 26 in good yield (scheme 9). [18] The RRM process in the presence of trans-butene and Grubbs-II catalyst cleanly afforded 27.…”

Section: Synthesis Of 2-hydroxyalkyl Piperidines Via a Nitroso Diels-mentioning

confidence: 99%

The Pivotal Role of N‐O bonds in the Synthesis of Natural Products: A mini‐review

Kouklovsky

2020

Vietnam Journal of Chemistry

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This review focuses on the role of the nitrogen‐oxygen bond as a structural cornerstone for the construction of complex natural products. This bond may play several roles such as a functional protecting group or an activating group in carbonyl chemistry. Compounds containing a N‐O bond are generally prepared by cycloaddition of nitroso derivatives, nitrones or nitriles oxides. The first two reactions have been used in the synthesis of a N‐O bond containing natural product, pyrinodemin A, or for the synthesis of hydroxylated piperidine alkaloids after N‐O bond cleavage.

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Stereodivergent Synthesis of Substituted N,O‐Containing Bicyclic Compounds by Sequential Addition of Nucleophiles to N‐Alkoxybicyclolactams

Cited by 90 publications

References 71 publications

Chemoselective Reductive Nucleophilic Addition to Tertiary Amides, Secondary Amides, and N‐Methoxyamides

Chemoselective Reductive Nucleophilic Addition to Tertiary Amides, Secondary Amides, and N‐Methoxyamides

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

The Pivotal Role of N‐O bonds in the Synthesis of Natural Products: A mini‐review

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