Enantioselective Approach to Quinolizidines: Total Synthesis of Cermizine D and Formal Syntheses of Senepodine G and Cermizine C

Veerasamy, Nagarathanam; Carlson, Erik C.; Collett, Nathan D.; Saha, Mrinmoy; Carter, Rich G.

doi:10.1021/jo400324t

Cited by 38 publications

(19 citation statements)

References 153 publications

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“…8 We also developed an organocatalyzed Michael reaction for accessing the lycopodine architectures. 9 Subsequently, we utilized these technologies to develop routes for the total synthesis of cermizine D (16), 10 formal syntheses of cermizine C (15) and senepodine G (the biosynthetic precursor of cermizine C) 11 and total syntheses of 10-hydroxylycopodium alkaloids 5-7. 12 Scheme 1 Correlation of related members of Lycopodium alkaloids within himeradine A…”

Section: Generalized Strategymentioning

confidence: 99%

Lycopodium Alkaloids: An Intramolecular Michael Reaction Approach

Saha¹,

Carter²

2017

Synlett

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The Lycopodium alkaloids possess a rich history that has captured the attention of synthetic chemists across the globe. This large family consists of over 250 known natural products with diverse structural features and noteworthy biological activity. Herein, we interweave the synthetic accomplishments by others in the field with our own unified strategy to accessing multiple subfamilies of the Lycopodium alkaloids. This discussion includes lycopodine, the C10-hydroxy Lycopodium alkaloids (10-hydroxylycopodine, deacetylpaniculine and paniculine), pelletierine, cermizine D, fastigiatine, himeradine A, clavolonine and 7-hydroxylycopodine. A unifying feature of much of the work discussed within this account is the use of intramolecular Michael additions to construct key ring systems within the Lycopodium alkaloids. Examples include the use of an intramolecular keto-sulfone Michael reaction and an intramolecular heteroatom Michael reaction.1 General Background on Lycopodium Alkaloids2 Development of a Strategy for Lycopodium Alkaloids2.1 Generalized Strategy2.2 Known Syntheses of C10-Functionalized Lycopodium Alkaloids3 Quinolizidine-Type Alkaloids3.1 Background3.2 Development of the Heteroatom Michael Reaction3.3 Synthesis of the Core Lycopodine Building Block: Pelletierine3.4 Total Synthesis of Cermizine D3.5 Synthesis of the Eastern Half of Himeradine A4 Lycopodine-Type Alkaloids4.1 Total Syntheses of Lycopodine4.1.1 Earlier Racemic Syntheses4.1.2 Approach Toward the Tricyclic Skeleton of Lycopodine: Intramolecular Mannich4.1.3 Enantioselective Total Syntheses of Lycopodine4.2 Total Syntheses of Clavolonine (8-Hydroxylycopodine)4.3 Total Synthesis of 7-Hydroxylycopodine4.4 Synthetic Route for 10-Hydroxy Lycopodium Alkaloids4.4.1 Background4.4.2 Total Syntheses4.4.3 Impact of the C10-Stereochemistry5 Conclusion

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Section: Generalized Strategymentioning

confidence: 99%

Lycopodium Alkaloids: An Intramolecular Michael Reaction Approach

Saha¹,

Carter²

2017

Synlett

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“…From the family of lycopodium alkaloids are worth to mention (−)-Cermizine C ( 60 ) and (+)-cermizine D ( 62 ), both isolated from the club moss Lycopodium cernuum and the related alkaloid (−)-senepodine G ( 61 ) from the club moss Lycopodium chinense ( Figure 5 ); the second latter displaced modest cytotoxicity against murin lymphoma L1210 cells. 60 was synthesized from 61 by reduction with NaBH 4 , while the synthesis of the latter was accomplished starting from 1 [ 47 , 48 ]. Enantioselective synthesis of 62 exploited the use of N -Boc 2 as common intermediate to access two of the three piperidine rings [ 49 ].…”

Section: A General Overview Of the Structures Of Alkaloids Synthesmentioning

confidence: 99%

Enzymatic Kinetic Resolution of 2-Piperidineethanol for the Enantioselective Targeted and Diversity Oriented Synthesis

Perdicchia

Christodoulou

Fumagalli

et al. 2015

IJMS

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2-Piperidineethanol (1) and its corresponding N-protected aldehyde (2) were used for the synthesis of several natural and synthetic compounds. The existence of a stereocenter at position 2 of the piperidine skeleton and the presence of an easily-functionalized group, such as the alcohol, set 1 as a valuable starting material for enantioselective synthesis. Herein, are presented both synthetic and enzymatic methods for the resolution of the racemic 1, as well as an overview of synthesized natural products starting from the enantiopure 1.

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“…Even though the synthesis was efficient and elegant, the starting material is expensive and its synthesis not trivial. Other attempts were either based on long reaction sequencesor used auxiliary chemistry to introduce the desired stereochemistry 23,24…”

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confidence: 99%

“…Other attempts were either based on long reaction sequencesor used auxiliary chemistry to introduce the desired stereochemistry. 23 , 24 …”

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confidence: 99%

Transition metal catalyzed stereodivergent synthesis of syn- and anti-δ-vinyl-lactams: formal total synthesis of (−)-cermizine C and (−)-senepodine G

Schmidt

Breit

2019

Chem. Sci.

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Enantioselective Approach to Quinolizidines: Total Synthesis of Cermizine D and Formal Syntheses of Senepodine G and Cermizine C

Cited by 38 publications

References 153 publications

Lycopodium Alkaloids: An Intramolecular Michael Reaction Approach

Lycopodium Alkaloids: An Intramolecular Michael Reaction Approach

Enzymatic Kinetic Resolution of 2-Piperidineethanol for the Enantioselective Targeted and Diversity Oriented Synthesis

Transition metal catalyzed stereodivergent synthesis of syn- and anti-δ-vinyl-lactams: formal total synthesis of (−)-cermizine C and (−)-senepodine G

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