Solanidine

Last updated
Solanidine
Solanidine.svg
Names
IUPAC name
Solanid-5-en-3β-ol
Systematic IUPAC name
(2S,4aR,4bS,6aS,6bR,7S,7aR,10S,12aS,13aS,13bS)-4a,6a,7,10-Tetramethyl-2,3,4,4a,4b,5,6,6a,6b,7,7a,8,9,10,11,12a,13,13a,13b,14-icosahydro-1H-naphtho[2′,1′:4,5]indeno[1,2-b]indolizin-2-ol
Other names
Solatubin; Solatubine
Identifiers
3D model (JSmol)
45370
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.191 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 201-309-5
KEGG
PubChem CID
UNII
  • InChI=1S/C27H43NO/c1-16-5-8-23-17(2)25-24(28(23)15-16)14-22-20-7-6-18-13-19(29)9-11-26(18,3)21(20)10-12-27(22,25)4/h6,16-17,19-25,29H,5,7-15H2,1-4H3/t16-,17+,19-,20+,21-,22-,23+,24-,25-,26-,27-/m0/s1
    Key: JVKYZPBMZPJNAJ-OQFNDJACSA-N
  • InChI=1/C27H43NO/c1-16-5-8-23-17(2)25-24(28(23)15-16)14-22-20-7-6-18-13-19(29)9-11-26(18,3)21(20)10-12-27(22,25)4/h6,16-17,19-25,29H,5,7-15H2,1-4H3/t16-,17+,19-,20+,21-,22-,23+,24-,25-,26-,27-/m0/s1
    Key: JVKYZPBMZPJNAJ-OQFNDJACBI
  • C[C@H]1CC[C@@H]2[C@H]([C@H]3[C@@H](N2C1)C[C@@H]4[C@@]3(CC[C@H]5[C@H]4CC=C6[C@@]5(CC[C@@H](C6)O)C)C)C
  • C[C@@H]1CN2[C@@]3([H])C[C@@]4([H])[C@]5([H])CCC6=C[C@@H](O)CC[C@]6(C)[C@@]5([H])CC[C@]4(C)[C@@]3([H])[C@H](C)[C@@]2([H])CC1
Properties
C27H43NO
Molar mass 397.647 g·mol−1
Hazards [1]
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H413
P264, P270, P273, P301+P312, P330, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Solanidine is a poisonous steroidal alkaloid chemical compound that occurs in plants of the family Solanaceae, such as potato and Solanum americanum . [2] [3] The sugar portion of glycoalkaloids hydrolyses in the body, leaving the solanidine portion. [4]

Contents

Occurrence

Solanidine is the hydrolyzed form [4] of several naturally occurring compounds all found in the Solanaceae family, such as glycoalkaloids, α-solanine and α-chaconine. [5] [4] Solanidine is not commonly found in nature, but precursors to it are. Glycoalkaloids are one of the toxins present in Solanum dulcamara and can be found in other Solanum plants as well such as potatoes, tomatoes and eggplant. Solanine is also found in all parts of the Solanum family species and is considered part of the plant's natural defenses. Chaconine is found in specifically green tubers and gives them their bitter taste. Solanidine is found naturally occurring in green potatoes and in the Solanum americanum [2] [3] species. The theorized biosynthetic route for the creation of Solanidine proposed in 1977 within the Solanaceae family was thought to be derived from cholesterol to the SA aglycone. This pathway was overturned in 2013 when a set of glycoalkaloid metabolism genes was found present in Solanaceae plants that participate in a SGA biosynthesis pathway. [6] [7]

Poisoning symptoms

Solanidine occurs in the blood serum of normal healthy people who eat potato, and serum solanidine levels fall markedly once potato consumption ceases. [8] Solanidine from food is also stored in the human body for prolonged periods of time, and it has been suggested that it could be released during times of metabolic stress with the potential for deleterious consequences. [9] Solanidine is responsible for neuromuscular syndromes via cholinesterase inhibition. [10] [11] Symptoms of cholinesterase inhibition include insomnia, nausea and vomiting, accidental injury, headache, dizziness, bradycardia, hypotension, ecchymosis, and sleep disturbance. [12] Solanidine poisoning is rarely fatal, but can in very severe cases cause coma and death. [13]

Uses

Solanidine to DPA synthesis

Solanidine is a very important precursor for the synthesis of hormones and some pharmacologically active compounds. [2] The idea to utilize Solanidine as a starting material came from a desire to utilize wasted potato glycoalkaloids from potato farming. It was found a successful starting material for the creation of steroid hormones, such as 16-DPA, which is a common intermediate found in industry synthesis of progesterone and cortisone derivatives. [14] The final reaction consisted of nine steps to get from Solanidine to DPA with a 30% yield.

Solanidine as a biomarker for CYP2D6 activity

Solanidine was found to have a strong biomarker in relation to the varied cytochrome gene CYP2D6. Due to its natural variance CYP2D6 can affect the efficiency and safety of common medicines such as antidepressants and antipsychotics. [15] Solanidine was first found to be a biomarker in 2014 and was notably absent in CYP2D6 poor metabolizers as well as in patients utilizing CYP2D6 inhibitors. Using paroxetine, a CYP2D6 inhibitor, 95% of solanidine metabolism was stopped. Since consumption of potatoes is so common, solanidine can be used as a biomarker when studying CYP2D6 drug-drug interactions and improve CYP2D6 activity prediction. [15]


Solanidine to 16-DPA conversion

Electrochemical oxidation of Solanidine: Electrochemical oxidation of Solanidine.svg
Electrochemical oxidation of Solanidine:

In 1994, Gunic and coworkers reported the electrochemical oxidation of 3β-acetoxy-solanidine in CH3CN/CH2Cl2 1/1 with pyridine as a base. The corresponding iminium salts 2 and 3 were obtained in a 1/1 ratio in good yield. Performing this electrochemical reaction in DCM with pyridine gives 3 in 95% yield, while the same reaction in acetone gives iminium salt 2 in 95% yield. Iminium ion 2 can be isomerized to the thermodynamically more stable enamine 5. THis isomerization is believed to proceed via enamine 4, which is the kinetic product.

Solanidine to 16-DPA conversion: Solanidine to 16-DPA conversion.svg
Solanidine to 16-DPA conversion:

In 1997, Gaši et al. reported a short procedure for the degradation of solanidine to 16-Dehydropregnenolone acetate. Instead of applying the electrochemical oxidation, Hg(OAc)2 in acetone was used as oxidizing agent. The advantage of this reagent and solvent system was the ease of use and the selective formation of iminium salt 2, which spontaneously isomerized to enamine 3 (94%). This enamine was then subjected to another isomerization, which yielded the more thermodynamically more stable enamine 4. NaIO4-oxidation opened up the cyclic enamine and gave lactam 5. Elimination of the lactam part with Al2O3 in benzene afforded in 34% 16-dehydropregnenolone acetate (DPA) (6). Using K2CO3 in benzene followed by reacetylation produced 6 in a lower yield (11%).

Solanidine to tomatidenol conversion

Solanidine von Braun reaction Solanidine von Braun.svg
Solanidine von Braun reaction

In 1968, Beisler and Sato synthesized tomatidenol from solanidine, and reported the successful opening of the E ring of solanidine via the von Braun reaction. [18] [19] Only in case of acetylated solanidine the von Braun reaction gave the E ring-opened product in 78% yield.

Schramm reaction Schramm reaction.svg
Schramm reaction

Treatment of α-bromine with KOAc gave in good yield the β-diacetate, which could be reduced with red-Al in benzene.

Schreiber reaction: Schreiber reaction.svg
Schreiber reaction:

These types of compounds can be ringclosed to spirosolane compounds as shown by Schreiber.

See also

Related Research Articles

<span class="mw-page-title-main">Potato</span> Staple food, root tuber, starchy

The potato is a starchy root vegetable native to the Americas that is consumed as a staple food in many parts of the world. Potatoes are tubers of the plant Solanum tuberosum, a perennial in the nightshade family Solanaceae.

<span class="mw-page-title-main">Solanine</span> Glycoalkaloid poison found in the nightshade family of plants

Solanine is a glycoalkaloid poison found in species of the nightshade family within the genus Solanum, such as the potato, the tomato, and the eggplant. It can occur naturally in any part of the plant, including the leaves, fruit, and tubers. Solanine has pesticidal properties, and it is one of the plant's natural defenses. Solanine was first isolated in 1820 from the berries of the European black nightshade, after which it was named. It belongs to the chemical family of saponins.

<span class="mw-page-title-main">Glycoalkaloid</span> Class of chemical compounds

Glycoalkaloids are a family of chemical compounds derived from alkaloids to which sugar groups are appended. Several are potentially toxic, most notably the poisons commonly found in the plant species Solanum dulcamara and other plants in the genus Solanum, including potato.

<i>Solanum lycocarpum</i> Species of flowering plant

Solanum lycocarpum, or wolf apple, is common in the Brazilian savanna, the Cerrado ecoregion. The plant is called lobeira or fruta-do-lobo in Portuguese.

<i>Solanum aculeastrum</i> Species of plant

Solanum aculeastrum is commonly known as soda apple, sodaapple nightshade, goat apple, poison apple, or more ambiguously as "bitter-apple". It is a poisonous nightshade species from Africa and only distantly related to true apples. The term "soda apple" probably derives from "Sodom apple", modified due to the fruit's detergent properties.

<span class="mw-page-title-main">Ibogaine</span> Psychoactive substance found in plants in the family Apocynaceae

Ibogaine is a naturally occurring psychoactive substance found in plants in the family Apocynaceae such as Tabernanthe iboga, Voacanga africana, and Tabernaemontana undulata. It is a psychedelic with dissociative properties.

<i>Solanum americanum</i> Species of flowering plant in the nightshade family Solanaceae

Solanum americanum, commonly known as American black nightshade, small-flowered nightshade or glossy nightshade, is a herbaceous flowering plant of wide though uncertain native range. The certain native range encompasses the tropics and subtropics of the Americas, Melanesia, New Guinea, and Australia.

<span class="mw-page-title-main">Voacangine</span> Chemical compound

Voacangine is an alkaloid found predominantly in the root bark of the Voacanga africana tree, as well as in other plants such as Tabernanthe iboga, Tabernaemontana africana, Trachelospermum jasminoides, Tabernaemontana divaricata and Ervatamia yunnanensis. It is an iboga alkaloid which commonly serves as a precursor for the semi-synthesis of ibogaine. It has been demonstrated in animals to have similar anti-addictive properties to ibogaine itself. It also potentiates the effects of barbiturates. Under UV-A and UV-B light its crystals fluoresce blue-green, and it is soluble in ethanol.

<i>Solanum jamesii</i> Species of plant

Solanum jamesii is a species of nightshade. Its range includes the southern United States. All parts of the plant, and especially the fruit, are toxic, containing solanine when it matures. The tubers were/are eaten raw or cooked by several Native American tribes, but they require leaching and boiling in clay in order to be rendered edible. The tubers are small when compared to familiar varieties of S. tuberosum.

<span class="mw-page-title-main">Tomatine</span> Chemical compound

Tomatine is a glycoalkaloid, found in the stems and leaves of tomato plants, and in the fruits at much lower concentrations. Chemically pure tomatine is a white crystalline solid at standard temperature and pressure.

<span class="mw-page-title-main">Solasodine</span> Chemical compound

Solasodine is a poisonous alkaloid chemical compound that occurs in plants of the family Solanaceae such as potatoes and tomatoes. Solasonine and solamargine are glycoalkaloid derivatives of solasodine. Solasodine is teratogenic to hamster fetuses in a dose of 1200 to 1600 mg/kg. Literature survey reveals that solasodine has diuretic, anticancer, antifungal, cardiotonic, antispermatogenetic, antiandrogenic, immunomodulatory, antipyretic and various effects on central nervous system.

<span class="mw-page-title-main">Solasonine</span> Chemical compound

Solasonine is a glycoalkaloid that is found in Solanum plants of the family Solanaceae. Solasonine is a poisonous chemical compound when used at high levels. It is a glycoside of solasodine. Glycoalkaloids such as Solasonine have various applications including pharmacology, cancer treatments and even a role as a pesticide.

<span class="mw-page-title-main">Solamargine</span> Chemical compound

Solamargine is a cytotoxic chemical compound that occurs in plants of the family Solanaceae, such as potatoes, tomatoes, and eggplants. It has been also isolated from Solanum nigrum fungal endophyte Aspergillus flavus. It is a glycoalkaloid derived from the steroidal alkaloid solasodine.

<span class="mw-page-title-main">Chaconine</span> Chemical compound

α-Chaconine is a steroidal glycoalkaloid that occurs in plants of the family Solanaceae. It is a natural toxicant produced in green potatoes and gives the potato a bitter taste. Tubers produce this glycoalkaloid in response to stress, providing the plant with insecticidal and fungicidal properties. It belongs to the chemical family of saponins. Since it causes physiological effects on individual organism, chaconine is considered to be defensive allelochemical. Solanine is a related substance that has similar properties.

<i>Solanum seaforthianum</i> Species of flowering plant

Solanum seaforthianum, the Brazilian nightshade, is a flowering evergreen vine of the family Solanaceae native to tropical South America. As a member of the Solanum genus, it is related to such plants as the tomato and potato. It is characterized by clusters of four to seven leaves and can climb to a height of 6 m (20 ft) given enough room. It blooms in the mid to late summer with clusters of star-shaped purple inflorescence followed by scarlet marble-sized berries. The plant is highly heat resistant, but cannot tolerate frost conditions. The plant contains modest amounts of various tropane alkaloids such as atropine, scopolamine and hyoscyamine and should be considered mildly toxic and inedible. Promising molluscicidal and schistosomicidal activities were displayed for the S. seaforthianum extracts and fractions which are attributed to the glycoalkaloid content.

<span class="mw-page-title-main">Esculeoside A</span> Chemical compound

Esculeoside A is a spirosolane-type glycoside with the molecular formula C58H95NO29. The structure of this product is 3-Ο-β-lycotetraosyl (22S,23S,25S)-23-acetoxy-3β,27-dihydroxy-5α-spirosolane 27-Ο-β-D-glucopyranoside. Fujiwara and colleagues were the first to isolate esculeoside A from the ripe fruit of the Cherry tomato in 2002. Esculeoside A, along with many other steroidal alkaloid glycosides, have been shown to possess cytotoxic activity that could result in a variety of potential health benefits for humans.

<span class="mw-page-title-main">Steroidal alkaloid</span> Class of chemical compounds

Steroidal alkaloids have the basic steroidal skeleton with nitrogen-based functional groups attached to the skeleton. More specifically, they are distinguished by their tetracyclic cyclopentanoperhydrophenanthrene skeleton that marks their close relationship with sterols. They fall in two major categories: Solanum alkaloids and Veratrum alkaloids. A Steroidal alkaloid has also been found in Chonemorpha fragrans, 'chonemorphine' was used to treat intestinal infections in Wistar rats..

<span class="mw-page-title-main">Solanaceae</span> Family of flowering plants that includes tomatoes, potatoes and tobacco

The Solanaceae, or the nightshades, are a family of flowering plants that ranges from annual and perennial herbs to vines, lianas, epiphytes, shrubs, and trees, and includes a number of agricultural crops, medicinal plants, spices, weeds, and ornamentals. Many members of the family contain potent alkaloids, and some are highly toxic, but many—including tomatoes, potatoes, eggplant, bell and chili peppers—are used as food. The family belongs to the order Solanales, in the asterid group and class Magnoliopsida (dicotyledons). The Solanaceae consists of about 98 genera and some 2,700 species, with a great diversity of habitats, morphology and ecology.

Lenape (B5141-6) is a potato cultivar first released in 1967 and named after the Lenape Native American tribe, which had to be pulled from the market in 1970 after findings of its high glycoalkaloid content. It was bred by Wilford Mills of Pennsylvania State University in collaboration with the Wise Potato Chip Company. The Lenape potato was produced by crossing Delta Gold with a wild Peruvian potato known for its resistance to insects. It was selected for its high specific gravity and low sugar content which made it ideal for producing potato chips but it was also immune to potato virus A and resistant to common strains of late blight. It is of medium-late maturity and produces round, white tubers with shallow eyes.

<span class="mw-page-title-main">16-Dehydropregnenolone acetate</span> Chemical compound

16-Dehydropregnenolone acetate (16-DPA) is a chemical compound used as an intermediate or synthon in the production of many semisynthetic steroids. As 7-ACA is for cephalosporins and 6-APA is for penicillins, 16-DPA is for steroids. While it is not easy to synthesize, it is a convenient intermediate which can be made from other more available materials, and which can then be modified to produce the desired target compound.

References

  1. ↑ "Solanidine". pubchem.ncbi.nlm.nih.gov.
  2. 1 2 3 Nikolic, NC; Stankovic, MZ (2003). "Solanidine hydrolytic extraction and separation from the potato (Solanum tuberosum L.) vines by using solid-liquid-liquid systems". Journal of Agricultural and Food Chemistry. 51 (7): 1845–9. doi:10.1021/jf020426s. PMID   12643640.
  3. 1 2 Mohy-ud-dint, A., Khan,Z., Ahmad, M., Kashmiri, M.A. (2010). "Chemotaxonomic value of alkaloids in Solanum nigrum complex" (PDF). Pakistan Journal of Botany. 42 (1): 653–660.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. 1 2 3 Kuiper-Goodman, T., Nawrot, P.S., Solanine and Chaconine, IPCS Inchem
  5. ↑ Friedman, M; Henika, PR; MacKey, BE (2003). "Effect of feeding solanidine, solasodine and tomatidine to non-pregnant and pregnant mice". Food and Chemical Toxicology . 41 (1): 61–71. doi:10.1016/s0278-6915(02)00205-3. PMID   12453729.
  6. ↑ Itkin M, Heinig U, Tzfadia O, Bhide AJ, Shinde B, Cardenas PD, Bocobza SE, Unger T, Malitsky S, Finkers R, Tikunov Y, Bovy A, Chikate Y, Singh P, Rogachev I, Beekwilder J, Giri AP, Aharoni A. Biosynthesis of antinutritional alkaloids in solanaceous crops is mediated by clustered genes. Science. 2013 Jul 12;341(6142):175-9. doi: 10.1126/science.1240230. Epub 2013 Jun 20. PMID 23788733.
  7. ↑ Cobb BA. The history of IgG glycosylation and where we are now. Glycobiology. 2020 Mar 20;30(4):202-213. doi: 10.1093/glycob/cwz065. PMID 31504525; PMCID: PMC7109348.
  8. ↑ Harvey, M.H.; McMillan, M.; Morgan, M.R.A.; Chan, H. W. S. (1985). "Solanidine is Present in Sera of Healthy Individuals and in Amounts Dependent on their Dietary Potato Consumption". Human & Experimental Toxicology. 4 (2): 187–194. doi:10.1177/096032718500400209. PMID   4007882. S2CID   43011062.
  9. ↑ Claringbold, W. D. B.; Few, J. D.; Renwick, J. H. (1982). "Kinetics and retention of solanidine in man". Xenobiotica. 12 (5): 293–302. doi:10.3109/00498258209052469. PMID   7135998.
  10. ↑ Bushway, R.J., Savage, S.A., Ferguson, B.S., Inhibition of acetyl cholinesterase by solanaceous glycoalkaloids and alkaloids, American Potato Journal, Aug. 1987, Volume 64, Issue 8, pp 409-413
  11. ↑ Everist, S.L., Poisonous Plants of Australia, Angus and Robertson, 1974, ISBN   0207142289.
  12. ↑ "Prescribing information : Aricept" (PDF). FDA access data. Eisai Inc. and Pfizer Inc. 2012. Archived (PDF) from the original on 2016-02-21. Retrieved 6 May 2021.
  13. ↑ Br Med J 1979;2:1458 https://doi.org/10.1136/bmj.2.6203.1458-a
  14. ↑ Vronen, Patrick. (2003). The synthesis of 16-dehydropregnenolone acetate (DPA) from potato glycoalkaloids. Arkivoc. 2004. 24. 10.3998/ark.5550190.0005.203.
  15. 1 2 Kiiski et al. Human Genomics (2024) 18:11 https://doi.org/10.1186/s40246-024-00579-8
  16. ↑ Gunic, E.; Tabakovic, I.; Gasi, K. M.; Miljkovic, D.; Juranic, I. (1994). "Products and Mechanisms in the Anodic Oxidation of Solanidine-Type Steroidal Alkaloids". The Journal of Organic Chemistry. 59 (6): 1264–1269. doi:10.1021/jo00085a011.
  17. ↑ "16-Dehydropregnenolone acetate from solanidine". Journal of the Serbian Chemical Society . 62 (6). 1996-11-04. Archived from the original on 2021-10-08. Retrieved 2023-03-14.
  18. ↑ Beisler, J. A.; Sato, Y. (1968). "A degradation of the solonidane skeleton". Chemical Communications (16): 963–964. doi:10.1039/C19680000963.
  19. ↑ Beisler, J. A.; Sato, Y. (1971). "Chemistry of the solanidane ring system". Journal of the Chemical Society C: Organic: 149–152. doi:10.1039/J39710000149.
  20. ↑ DE 20217610,Schramm, Geza&Riedl, Horst,"Verfahren zur Herstellung von Piperidylsteroiden [Process for the manufacture of piperidyl steroids]",published 1971-11-25, assigned to Lentia GmbH
  21. ↑ Schreiber, Klaus; Rönsch, Hasso (1965). "Solanum-Alkaloide, XLIV über Tomatid-5-en-3ß-ol aus Solanum dulcamara L. Und dessen Abbau zu 3ß-Acetoxy-pregna-5.16-dien-20-on". Justus Liebigs Annalen der Chemie. 681: 187–195. doi:10.1002/jlac.19656810127.
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