The Hydroxylated, Tetracyclic Bisquinolizidine Alkaloids Baptifoline and Epibaptifoline: Enantioselective Synthesis and Unambiguous Assignment of their Configuration at C‐13

Goller, Jessica; Hübschle, Christian B.; Breuning, Matthias

doi:10.1002/ejoc.201801126

Cited by 7 publications

(13 citation statements)

References 38 publications

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“…By exploiting a similar strategy, the syntheses of tetracyclic alkaloids baptifoline and epibaptifoline were recently [34] developed (Scheme 18). Treating allyl‐cytisine 66 with aqueous formaldehyde in a phosphate buffer (pH=5), epibaptifoline 72 was obtained in high yields as a single diastereomer.…”

Section: Synthesis Of (−)‐Sparteine and Related Tetracyclic Systemsmentioning

confidence: 99%

Synthesis of Natural Compounds Based on the [3,7]‐Diazabicyclo[3.3.1]nonane (Bispidine) Core

Sacchetti

Rossetti

2021

Eur J Org Chem

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The [3,7]‐diazabicyclo[3.3.1]nonane (bispidine) structure is found in several interesting naturally occurring alkaloids. The most representative components are the tetracyclic alkaloid (−)‐sparteine and the tricyclic (−)‐cytisine alkaloids. Their biological activities have been known for a long time. In the literature, different syntheses of both tetracyclic and tricyclic structures have been reported, especially in the last few years, when a number of new reports renewed the interest in these fascinating molecules. Bicyclic bispidine derivatives have been thoroughly investigated in recent times also for their applications as catalysts, metal chelating agents, and lately in coordination polymers chemistry. In this review, we describe the most relevant strategies for the synthesis of molecules based on the [3,7]‐diazabicyclo[3.3.1]nonane core, related to (−)‐sparteine and (−)‐cytisine alkaloids.

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Section: Synthesis Of (−)‐Sparteine and Related Tetracyclic Systemsmentioning

confidence: 99%

Synthesis of Natural Compounds Based on the [3,7]‐Diazabicyclo[3.3.1]nonane (Bispidine) Core

Sacchetti

Rossetti

2021

Eur J Org Chem

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“…[19]: [α] D À 113.5 (c = 1.5, MeOH)} [29] . 1 H NMR (CDCl 3 , 500 MHz): δ = 7.27 (dd, J = 9.0 Hz, 6.9 Hz, 1 H, 4-H), 6.44 (m, 1 H, 12-H), 6.42 (m, 1 H, 5-H), 6.15 (d, J = 6.9 Hz, 1 H, 3-H), 6.12 (t, J = 3.1 Hz, 1 H, 14-H), 5.97 (m, 1 H, 13-H), 4.33 (dm, J = 14.5 Hz, 1 H, 10-HH), 4.28 (dd, J = 11.9 Hz, 4.2 Hz, 1 H, 16-HH), 4.10 (dm, J = 11.9 Hz, 1 H, 16-HH), 3.75 (dd, J = 14.5 Hz, 4.5 Hz, 1 H, 10-HH), 3.69 (m, 1 H, 9-H), 3.44 (m, 1 H, 7-H), 2.21 (dm, J = 13.0 Hz, 1 H, 8-HH), 2.16 (dm, J = 13.0 Hz, 1 H, 8-HH); 13…”

Section: Oxidation Of Cytisine (3)mentioning

confidence: 99%

“… Known [10,12,13] and current strategies for the total synthesis of bisquinolizidine and quinolizidine‐indolizidine alkaloids.…”

Section: Introductionmentioning

confidence: 99%

“…We recently presented an effective inside‐out approach to tri‐ and tetracyclic bisquinolizidine alkaloids that permits access to more than 25 members of this class in both enantiomeric forms (Scheme 1, top) [12–14] . Key sequences include the reductive desymmetrization of the bisimide 13 and the transformation of the resulting dioxobispidine 14 into the α, N ‐pyridone annulated tricycle 15 .…”

Section: Introductionmentioning

confidence: 99%

“…[6g] We recently presented an effective inside-out approach to tri-and tetracyclic bisquinolizidine alkaloids that permits access to more than 25 members of this class in both enantiomeric forms (Scheme 1, top). [12][13][14] Key sequences include the reductive desymmetrization of the bisimide 13 and the transformation of the resulting dioxobispidine 14 into the α,N-pyridone annulated tricycle 15. An important stereochemical feature is that the N-Boc activated lactam function in 15 allows an introduction of either an endo-or, optionally, an exo-fused ring by a simple change of the reaction order.…”

Section: Introductionmentioning

confidence: 99%

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Diastereodivergent Synthesis of the Quinolizidine‐Indolizidine Alkaloids of the Leontidine/Camoensine Family

et al. 2021

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Leontidine and camoensine, the main representatives of the small quinolizidine‐indolizidine alkaloid subgroup, are characterized by an inner bispidine system to which a 2‐pyridone and a pyrrolidine are fused on opposite sides. We efficiently synthesized both natural products from the commercially available and abundant alkaloid cytisine, which was converted into the key intermediate, N‐Boc‐11‐oxocytisine, by iodine oxidation and protection. Grignard addition, Paal‐Knorr type cyclization, and hydrogenation delivered endo‐pyrrolidine fused leontidine, while the reversed reaction order, viz. reduction, Sakurai allylation, and ring closure, afforded exo‐pyrrolidine annulated camoensine. Hydrogenation and deoxygenation of the pyridone moieties provided four further alkaloids, tetrahydroleontidine, camoensidine, 11‐epileontidane and leontidane. In addition, the artificial alkaloid isoleontidine, carrying an endo‐fused pyrrolidine on the same side as the pyridone, was prepared from C‐13 oxidized cytisine.

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Quinolizidine Alkaloids with Antitomato Spotted Wilt Virus and Insecticidal Activities from the Seeds of Thermopsis lanceolata R. Br

Zhang

Zou

et al. 2022

J. Agric. Food Chem.

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As part of our ongoing investigation of pesticide active quinolizidine alkaloids (QAs) from the family Fabaceae, the chemical constituents of the seeds of Thermopsis lanceolata R. Br. were systematically investigated. Bioassay-guided fractionation and purification of the crude extract led to the isolation of seventeen new QAs (1−17), including three new naturally occurring compounds (15−17), along with 15 known compounds (18−32). Their structures were elucidated by comprehensive spectroscopic data analysis (IR, UV, NMR, and HRESIMS) and quantum chemistry calculations ( 13 C NMR and ECD). The antitomato spotted wilt virus activities and insecticidal activities against Aphis fabae, Nilaparvata lugens (Stal), and Tetranychus urticae of compounds 1− 32 were screened using the lesion counting method, spray method, and rice-stem dipping method, respectively. Biological tests indicated that compounds 6, 9, 10, and 18 displayed significant anti-TSWV activities compared with the positive control ningnanmycin.

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The Hydroxylated, Tetracyclic Bisquinolizidine Alkaloids Baptifoline and Epibaptifoline: Enantioselective Synthesis and Unambiguous Assignment of their Configuration at C‐13

Cited by 7 publications

References 38 publications

Synthesis of Natural Compounds Based on the [3,7]‐Diazabicyclo[3.3.1]nonane (Bispidine) Core

Synthesis of Natural Compounds Based on the [3,7]‐Diazabicyclo[3.3.1]nonane (Bispidine) Core

Diastereodivergent Synthesis of the Quinolizidine‐Indolizidine Alkaloids of the Leontidine/Camoensine Family

Quinolizidine Alkaloids with Antitomato Spotted Wilt Virus and Insecticidal Activities from the Seeds of Thermopsis lanceolata R. Br

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