Solanidine is a poisonous steroidal alkaloid chemical compound that occurs in plants of the family Solanaceae, such as potato and Solanum americanum.[
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Occurrence
Solanidine is the hydrolyzed form[ of several naturally occurring compounds all found in the Solanaceae family, such as glycoalkaloids, α-solanine and α-chaconine.][Kuiper-Goodman, T., Nawrot, P.S., Solanine and Chaconine, IPCS Inchem] 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[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.][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.]
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.[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 [2]][Everist, S.L., Poisonous Plants of Australia, Angus and Robertson, 1974, .] Symptoms of cholinesterase inhibition include insomnia, nausea and vomiting, accidental injury, headache, dizziness, bradycardia, hypotension, ecchymosis, and sleep disturbance.[ "Prescribing information : Aricept"
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Uses
Solanidine to DPA synthesis
Solanidine is a very important precursor for the synthesis of hormones and some pharmacologically active compounds.[ 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.][Vronen, Patrick. (2003). The synthesis of 16-dehydropregnenolone acetate (DPA) from potato glycoalkaloids. Arkivoc. 2004. 24. 10.3998/ark.5550190.0005.203.] 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.[
/ref> Solanidine was first found to be a biomarker in 2014 and was found in high concentrations in CYP2D6 poor metabolizers as well as in patients utilizing CYP2D6 inhibitors compared with rapid metabolizers. 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.]
Solanidine to 16-DPA conversion
In 1994, Gunic and coworkers reported the electrochemical oxidation of 3β-acetoxy-solanidine in acetonitrile/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.
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 alumina 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
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.
See also
