Solanidine To 16-DPA Conversion on:
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Solanidine is a
Solanine and Chaconine
IPCS Inchem The sugar portion of these glycoalkaloids
In 1994 Gunic and coworkers reported the 
In 1997 Gaši ''et al.'' reported a short procedure for the degradation of solanidine to DPA. 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
In 1968 Beisler and Sato reported the successful opening of the E ring of solanidine via the 
Treatment of α-bromine with KOAc gave in good yield the β-diacetate, which could be reduced with 
These types of compounds can be ringclosed to spirosolane compounds as shown by Schreiber.
poisonous
Poison is a chemical substance that has a detrimental effect to life. The term is used in a wide range of scientific fields and industries, where it is often specifically defined. It may also be applied colloquially or figuratively, with a broa ...
steroidal alkaloid chemical
A chemical substance is a form of matter having constant chemical composition and characteristic properties. Some references add that chemical substance cannot be separated into its constituent elements by physical separation methods, i.e., w ...
compound
Compound may refer to:
Architecture and built environments
* Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall
** Compound (fortification), a version of the above fortified with defensive struc ...
that occurs in plants of the family Solanaceae, such as potato
The potato is a starchy food, a tuber of the plant ''Solanum tuberosum'' and is a root vegetable native to the Americas. The plant is a perennial in the nightshade family Solanaceae.
Wild potato species can be found from the southern Unit ...
and ''Solanum americanum
''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 subtr ...
''. Human ingestion of solanidine also occurs via the consumption of the glycoalkaloids, α-solanine
Solanine is a glycoalkaloid poison found in species of the nightshade family within the genus ''Solanum'', such as the potato (''Solanum tuberosum''), the tomato (''Solanum lycopersicum''), and the eggplant (''Solanum melongena''). It can occur ...
and α-chaconine, present in potatoes.Kuiper-Goodman, T., Nawrot, P.S.Solanine and Chaconine
IPCS Inchem The sugar portion of these glycoalkaloids
hydrolyses
Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile.
Biological hydrolysis ...
in the body, leaving the solanidine portion. Solanidine occurs in the blood serum of normal healthy people who eat potato, and serum solanidine levels fall markedly once potato consumption ceases. 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. Solanidine is responsible for neuromuscular
A neuromuscular junction (or myoneural junction) is a chemical synapse between a motor neuron and a muscle fiber.
It allows the motor neuron to transmit a signal to the muscle fiber, causing muscle contraction.
Muscles require innervation ...
syndromes via cholinesterase
The enzyme cholinesterase (EC 3.1.1.8, choline esterase; systematic name acylcholine acylhydrolase) catalyses the hydrolysis of choline-based esters:
: an acylcholine + H2O = choline + a carboxylate
Several of these serve as neurotransmitters ...
inhibition.Everist, S.L., ''Poisonous Plants of Australia'', Angus and Robertson, 1974, .
Uses
Solanidine is a very importantprecursor
Precursor or Precursors may refer to:
* Precursor (religion), a forerunner, predecessor
** The Precursor, John the Baptist
Science and technology
* Precursor (bird), a hypothesized genus of fossil birds that was composed of fossilized parts of u ...
for the synthesis of hormones and some pharmacologically active compounds.
Solanidine to
16-DPA
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 ...
In 1994 Gunic and coworkers reported the electrochemical
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
oxidation of 3β-acetoxy-solanidine in CH3CN/ CH2Cl2 1/1 with pyridine
Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakly alkaline, water-miscible liquid with a ...
as a base. The corresponding iminium salts 2 and 3 were obtained in a 1/1 ratio in good yield. Performing this electrochemical
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
reaction in DCM with pyridine gives 3 in 95% yield, while the same reaction in acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
gives iminium
In organic chemistry, an iminium cation is a polyatomic ion with the general structure . They are common in synthetic chemistry and biology.
Structure
Iminium cations adopt alkene-like geometries. The central C=N unit is nearly coplanar with al ...
salt 2 in 95% yield. Iminium
In organic chemistry, an iminium cation is a polyatomic ion with the general structure . They are common in synthetic chemistry and biology.
Structure
Iminium cations adopt alkene-like geometries. The central C=N unit is nearly coplanar with al ...
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 DPA. 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
In organic chemistry, an iminium cation is a polyatomic ion with the general structure . They are common in synthetic chemistry and biology.
Structure
Iminium cations adopt alkene-like geometries. The central C=N unit is nearly coplanar with al ...
salt 2, which spontaneously isomerized to enamine 3 (94%). This enamine
An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates.
:
The word "enamine" is derived from the affix ''en''-, used as the suffix of alkene, and t ...
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
In 1968 Beisler and Sato reported the successful opening of the E ring of solanidine via the von Braun reaction
The von Braun reaction is an organic reaction in which a tertiary amine reacts with cyanogen bromide to an organocyanamide.
An example is the reaction of ''N'',''N''-dimethyl-1-naphthylamine:
These days, most chemist have replaced cyanogen ...
. Only in case of acetylated solanidine the von Braun reaction gave the E ring-opened product in 78% yield.
Treatment of α-bromine with KOAc gave in good yield the β-diacetate, which could be reduced with Red-Al
Sodium bis(2-methoxyethoxy)aluminium hydride (SMEAH; trade names Red-Al, Synhydrid, Vitride) is a complex hydride reductant with the chemical formula, formula NaAlH2(OCH2CH2OCH3)2. The trade name Red-Al refers to its being a ''red''ucing ''al''um ...
in benzene.
These types of compounds can be ringclosed to spirosolane compounds as shown by Schreiber.
See also
*Solasodine
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 fetus ...
References
{{reflist Steroidal alkaloids Plant toxins Steroidal alkaloids found in Solanaceae Heterocyclic compounds with 6 rings Nitrogen heterocycles