Solanidine

Solanidine is a poisonous steroidal alkaloid chemical compound that occurs in plants of the family Solanaceae, such as potato and Solanum americanum.[2][3] Human ingestion of solanidine also occurs via the consumption of the glycoalkaloids, α-solanine and α-chaconine, present in potatoes.[4][5] The sugar portion of these glycoalkaloids hydrolyses in the body, leaving the solanidine portion.[5] Solanidine occurs in the blood serum of normal healthy people who eat potato, and serum solanidine levels fall markedly once potato consumption ceases.[6] 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.[7] Solanidine is responsible for neuromuscular syndromes via cholinesterase inhibition.[8][9]

Solanidine
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
EC Number
  • 201-309-5
KEGG
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:
GHS07: Exclamation mark
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).
Infobox references

Uses

Solanidine is a very important precursor for the synthesis of hormones and some pharmacologically active compounds.[2]

Synthetic uses

Solanidine to 16-DPA conversion
Electrochemical oxidation of Solanidine:[10]

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:[11]

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

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.[12][13] Only in case of acetylated solanidine the von Braun reaction gave the E ring-opened product in 78% yield.

Schramm reaction[14]

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

Schreiber reaction:[15]

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

See also

References
  1. "Solanidine". pubchem.ncbi.nlm.nih.gov.
  2. 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. 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. 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.
  5. Kuiper-Goodman, T., Nawrot, P.S., Solanine and Chaconine, IPCS Inchem
  6. 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.
  7. 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.
  8. 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
  9. Everist, S.L., Poisonous Plants of Australia, Angus and Robertson, 1974, ISBN 0207142289.
  10. 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.
  11. "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.
  12. Beisler, J. A.; Sato, Y. (1968). "A degradation of the solonidane skeleton". Chemical Communications (16): 963. doi:10.1039/C19680000963.
  13. Beisler, J. A.; Sato, Y. (1971). "Chemistry of the solanidane ring system". Journal of the Chemical Society C: Organic: 149. doi:10.1039/J39710000149.
  14. 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
  15. 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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