Studies on the Synthesis of Phlegmarine-Type <i>Lycopodium</i> Alkaloids: Enantioselective Synthesis of (−)-Cermizine B, (+)-Serratezomine E, and (+)-Luciduline

Pinto, Alexandre; Piccichè, Miriam; Griera, Rosa; Molins, Elı́es; Bosch, Joan; Amat, Mercedes

doi:10.1021/acs.joc.8b00983

Cited by 13 publications

(9 citation statements)

References 68 publications

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“… Synthesis of precursors to alkaloids can also be achieved using this reaction (Scheme ). , In both of these cases, the allyl group was used to form a six-membered ring with the homoallylic nitrogen atom by ring-closing metathesis. The allylation reaction has also been used to prepare amines that have been examined for their use for the synthesis of macrolide antibiotic analogues (Scheme ).…”

Section: Additions Of Allylmagnesium Reagents To Imines and Related S...mentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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This review describes the additions of allylmagnesium reagents to carbonyl compounds and to imines, focusing on the differences in reactivity between allylmagnesium halides and other Grignard reagents. In many cases, allylmagnesium reagents either react with low stereoselectivity when other Grignard reagents react with high selectivity, or allylmagnesium reagents react with the opposite stereoselectivity. This review collects hundreds of examples, discusses the origins of stereoselectivities or the lack of stereoselectivity, and evaluates why selectivity may not occur and when it will likely occur. CONTENTS 4.2.5. Additions to β-Substituted Aldehydes 4.2.6. Additions to Aldehydes with Distant Chelating Groups 4.3. Additions to Cyclic Ketones 4.3.1. Alkoxy-Substituted Cyclic Ketones 4.3.2. Additions to Alkoxy-Substituted Five-Membered-Ring Ketones 4.3.3. Additions to Alkoxy-Substituted Four-Membered-Ring Ketones 4.4. Additions of Allylmagnesium Halides to Cyclic Hemiacetals 5. Diastereoselectivity of Reactions of Allylmagnesium Reagents with Carbonyl Compounds by Felkin−Anh Control 5.1. Felkin−Anh Stereoselectivity 5.2. Additions to α-Chiral Acyclic Ketones 5.3. Additions to Chiral Exocyclic Ketones and Aldehydes 5.4. Additions of Allylmagnesium Halides to Chiral Cyclic Ketones Controlled by Felkin−Anh Selectivity 5.5. Additions of Allylmagnesium Halides to Chiral Acyclic Aldehydes 6. Diastereoselectivity of Reactions with Carbonyl Compounds by Steric Approach Control 6.1. Steric Approach Control and Stereoselectivity

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Section: Additions Of Allylmagnesium Reagents To Imines and Related S...mentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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“…In 2017, Reddy and co-workers described the stereoselective synthesis of (S)-1-benzyl-6,7-dimethoxy-1,2,3,4-tetrahydroiso-quinoline ( 163), (S)-1-benzyl-6,7-dimethoxy-N-methyl-1,2,3,4tetrahydroisoquinoline ( 164 quent steps, including ring-closing metathesis [133], (−)-cermizine B ( 171) and (+)-serratezomine E (172) were obtained 57% and 72% yield, respectively (Scheme 43) [134,135].…”

Section: Cyclizations Involving a Position In The Starting Chiral Iminementioning

confidence: 99%

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Mendes¹,

Costa²,

Yus³

et al. 2021

Beilstein J. Org. Chem.

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The synthesis of nitrogen-containing heterocycles, including natural alkaloids and other compounds presenting different types of biological activities have proved to be successful employing chiral sulfinyl imines derived from tert-butanesulfinamide. These imines are versatile chiral auxiliaries and have been extensively used as eletrophiles in a wide range of reactions. The electron-withdrawing sulfinyl group facilitates the nucleophilic addition of organometallic compounds to the iminic carbon with high diastereoisomeric excess and the free amines obtained after an easy removal of the tert-butanesulfinyl group can be transformed into enantioenriched nitrogen-containing heterocycles. The goal of this review is to the highlight enantioselective syntheses of heterocycles involving the use of chiral N-tert-butanesulfinyl imines as reaction intermediates, including the synthesis of several natural products. The synthesis of nitrogen-containing heterocycles in which the nitrogen atom is not provided by the chiral imine will not be considered in this review. The sections are organized according to the size of the heterocycles. The present work will comprehensively cover the most pertinent contributions to this research area from 2012 to 2020. We regret in advance that some contributions are excluded in order to maintain a concise format.

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“…In recent work we have explored the stereoselective generation of chiral aminoalcohol-derived oxazoloquinolone tricyclic lactams and their transformation into diversely substituted cis -decahydroquinolines (DHQs). The relevance of these enantiomeric scaffolds in the total synthesis of alkaloids having in common a DHQ nucleus was illustrated with the total synthesis of Myrioneuron , Lycopodium , amphibian, and marine alkaloids . To further demonstrate the synthetic utility of these chiral tricyclic lactams, we decided to undertake the more challenging total synthesis of cylindricine H, which requires the formation of a quaternary carbon center embedded within a complex azatricyclic system.…”

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confidence: 99%

Total Synthesis of (−)-Cylindricine H

et al. 2022

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Starting from (R)-phenylglycinol-derived tricyclic lactam 1, the enantioselective synthesis of (−)-cylindricine H is reported. From the stereochemical standpoint, the key steps are the stereoselective generation of the quaternary C 10 stereocenter, the stereoselective introduction of the C 4 acetoxy and C 2 butyl substituents taking advantage of the lactam carbonyl functionality, and the assembly of the pyrrolidine ring with the required functionalized one-carbon chain at C 13 by intramolecular opening of an epoxide.

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Studies on the Synthesis of Phlegmarine-Type Lycopodium Alkaloids: Enantioselective Synthesis of (−)-Cermizine B, (+)-Serratezomine E, and (+)-Luciduline

Cited by 13 publications

References 68 publications

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Total Synthesis of (−)-Cylindricine H

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