Carbamate‐Catalyzed Enantioselective Bromolactamization

Yi, Cheng; Yu, Wesley Zongrong; Yeung, Ying‐Yeung

doi:10.1002/anie.201504724

Cited by 62 publications

(21 citation statements)

References 52 publications

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“…Strains of the human parasite Plasmodium falciparum resistant to the quinine and its analogs are widespread, and the prevalence of multiple types of drug‐resistant P. falciparum strains has severely limited the use of quinines to treat malaria . Besides its use as the lead compound for the preparation of catalysts and ligands which can effectively catalyze the reactions such as Michael/Mannich, aza‐Henry, cycloaddition, and asymmetric olefin isomerization, quinine ( i ) has also exhibited numerous interesting insecticidal and antibacterial activities . However, systematic research on structure optimizations and structure–activity relationship (SAR) of quinidine derivatives as insecticidal agents has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Che

Yang

Sun

et al. 2020

Chemistry & Biodiversity

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Endeavor to discover biorational natural products-based insecticides, two series (30) of novel (9S)-acyloxy derivatives of quinidine and dihydroquinidine were prepared and assessed for their insecticidal activity against Mythimna separata in vivo by the leaf-dipping method at 1 mg/mL. Among all the compounds, especially four derivatives exhibited the best insecticidal activity with final mortality rates of 71.4 %, 75.0 %, 71.4 %, and 75.0 %, respectively. Relatively speaking, 9-hydroxy group is well tolerated, and the results showed that after modification of the hydroxy group with an acyloxy group, the insecticidal activity was significantly increased; the configuration at C8/9 position is important for insecticidal activity, and the (9S)-configuration is optimal; modification of the out-ring double bond is acceptable, and hydrogenation of the double bond enhances insecticidal activity. These preliminary results will pave the way for further modification of quinidine in the development of potential new insecticides.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Che

Yang

Sun

et al. 2020

Chemistry & Biodiversity

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“…Bromolactamization of olefinic amide is another catalytic and enantioselective N‐cyclization protocol that we successfully devised using carbamate organocatalysts (Scheme ) . The major obstacle in this type of reaction is the inherent tendency for olefinic amide to undergo O‐cyclization instead of N‐cyclization because the oxygen atom has a higher electronegativity than the nitrogen atom…”

Section: Thiocarbamate and Carbamate Catalystsmentioning

confidence: 99%

Lewis Base Catalyzed Stereo‐ and Regioselective Bromocyclization

Gieuw

Yeung

2016

The Chemical Record

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Oxygen- and nitrogen-containing heterocyclic compounds are widely recognized as key components in many natural products and biologically relevant molecules, but often the problem comes down to methodologies in synthesizing them. Halocyclization of olefinic substrates is a promising strategy in the construction of O- and N-heterocyclic compounds, which further signifies the development of their asymmetric variants. Over the past years, our group has been devoted to this particular area of asymmetric electrophilic halocyclization with chalcogen-containing molecules as catalysts. In this account, the main focus is on the development of our novel chiral catalysts and applications derived from the reaction products.

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“…In order to achieve CO 2 -capture with an unsaturated alcohol or amine ( 1 ) (Scheme 1A), alkene haloetherification and haloamination pathways (Scheme 1B, blue boxes) must be subverted by an intermolecular CO 2 -capture step (Scheme 1B). 12 Indeed, enantioselective halofunctionalizations of alkenes with both oxygen 8,13,14,15 and nitrogen 16 nucleophiles have witnessed success in recent years. Electron-withdrawing groups (EWG) at nitrogen enable N-C bond formation with an activated alkene, but cannot be employed as a design element here (Scheme 1A, R’=EWG), as it would slow, if not prevent CO 2 -capture.…”

Section: Introductionmentioning

confidence: 99%

Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl Amines by CO₂-Capture: Discovery, Development, and Mechanism

et al. 2018

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Cyclic carbamates are a common feature of small molecule therapeutics, offering a constrained hydrogen bond acceptor that is both polar and sterically small. Methods for their preparation most often focus first on aminoalcohol synthesis and then reaction with phosgene or its equivalent. This report describes an enantioselective synthesis of cyclic carbamates in which carbon dioxide engages an unsaturated basic amine, facilitated by a bifunctional organocatalyst designed to stabilize a carbamic acid intermediate while activating it toward subsequent enantioselective carbon-oxygen bond formation. Six-membered cyclic carbamates are prepared in good yield with high levels of enantioselection, as constrained 1,3-amino alcohols featuring a chiral tertiary alcohol carbon. Spectroscopic analysis (NMR, DOSY) of various substrate-reagent combinations provides insight into the dominant species under the reaction conditions. Two peculiar requirements were identified to achieve highest consistency: a ‘Goldilocks’ amount of water and the use of a non-crystalline form of the ligand. These atypical features of the final protocol notwithstanding, a diverse range of products could be prepared. Their functionalizations illustrate the versatility of the carbamates as precursors to enantioenriched small molecules.

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Carbamate‐Catalyzed Enantioselective Bromolactamization

Cited by 62 publications

References 52 publications

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Lewis Base Catalyzed Stereo‐ and Regioselective Bromocyclization

Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl Amines by CO₂-Capture: Discovery, Development, and Mechanism

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Carbamate‐Catalyzed Enantioselective Bromolactamization

Cited by 62 publications

References 52 publications

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Synthesis of Novel (9S)‐Acyloxy Derivatives of Quinidine and Dihydroquinidine as Insecticidal Agents

Lewis Base Catalyzed Stereo‐ and Regioselective Bromocyclization

Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl Amines by CO2-Capture: Discovery, Development, and Mechanism

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Catalytic, Enantioselective Synthesis of Cyclic Carbamates from Dialkyl Amines by CO₂-Capture: Discovery, Development, and Mechanism