550-90-3

Usage

Uses

Used in Biological Studies:
Lupanine is utilized as a subject of study in the field of biological research, particularly focusing on quinolizidine alkaloids found in the seeds of lupin genotypes from different origins. This research contributes to the understanding of the properties and potential applications of these alkaloids.
Used in Pharmaceutical Industry:
Lupanine is used as a pharmaceutical compound due to its unique chemical structure and properties. Its study and potential applications in the pharmaceutical industry could lead to the development of new drugs and therapies.
Used in Agricultural Research:
As lupanine is derived from the seeds of lupin genotypes, it is also used in agricultural research to understand the genetic and environmental factors that influence the production and quality of these alkaloids in lupin plants. This knowledge can be applied to improve crop cultivation and yield.

InChI:InChI=1/C15H24N2O/c18-15-6-3-5-14-11-8-12(10-17(14)15)13-4-1-2-7-16(13)9-11/h11-14H,1-10H2/t11-,12-,13+,14-/m0/s1

Synthetic route

(1S,2R,9S,10S)-7,15-diazatetracyclo[7.7.1.02,7.010,15]heptadec-12-en-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr; for 2.5h;	93%

L-(-)-lupanine D-tartrate salt → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	30%

D-(+)-lupanine-L-tartrate → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	19%

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → (+)-lupanine (550-90-3)

Conditions	Yield
With sodium tetrahydroborate; formic acid; sulfur dioxide Ambient temperature; other N-oxides of sparteine lactams;
With hydrogen; platinum(IV) oxide In acetic acid under 760 Torr; for 1h; Product distribution; other N-oxides of sparteine lactams; other times;

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → 17-hydroxylupanine + (+)-lupanine (550-90-3)

Conditions	Yield
With formic acid; sulfur dioxide for 0.5h; Mechanism; Product distribution; Ambient temperature; other N-oxides of sparteine lactams; other times;

5,6-dehydrolupanine (32101-29-4) → (+)-lupanine (550-90-3)

Conditions	Yield
With hydrogen; palladium on activated charcoal In ethanol	3.2 mg
With hydrogen; palladium on activated charcoal In ethanol Ambient temperature;

(+)-lupanine N-oxide → (+)-lupanine (550-90-3)

Conditions	Yield
With sulfur dioxide In methanol at 0℃; for 0.25h;	4 mg

hydrogen iodide (10034-85-2) + 13α-hydroxylupanine (15358-48-2) + red phosphorus → (+)-lupanine (550-90-3)

13α-hydroxylupanine (15358-48-2) + phosphorus pentoxide → water (7732-18-5) + (+)-lupanine (550-90-3)

Conditions	Yield
at 170℃; folgende Hydrierung;

6β-hydroxylupanine → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: CHCl3 / 12 h / Ambient temperature 2: 3.2 mg / H2 / 5percent Pd-C / ethanol View Scheme

(1S,2R,9S,10S)-7,15-diazatetracyclo[7.7.1.02,7.010,15]heptadec-12-en-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr; for 2.5h;	93%

L-(-)-lupanine D-tartrate salt → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	30%

D-(+)-lupanine-L-tartrate → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	19%

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → (+)-lupanine (550-90-3)

Conditions	Yield
With sodium tetrahydroborate; formic acid; sulfur dioxide Ambient temperature; other N-oxides of sparteine lactams;
With hydrogen; platinum(IV) oxide In acetic acid under 760 Torr; for 1h; Product distribution; other N-oxides of sparteine lactams; other times;

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → 17-hydroxylupanine + (+)-lupanine (550-90-3)

Conditions	Yield
With formic acid; sulfur dioxide for 0.5h; Mechanism; Product distribution; Ambient temperature; other N-oxides of sparteine lactams; other times;

5,6-dehydrolupanine (32101-29-4) → (+)-lupanine (550-90-3)

Conditions	Yield
With hydrogen; palladium on activated charcoal In ethanol	3.2 mg
With hydrogen; palladium on activated charcoal In ethanol Ambient temperature;

(+)-lupanine N-oxide → (+)-lupanine (550-90-3)

Conditions	Yield
With sulfur dioxide In methanol at 0℃; for 0.25h;	4 mg

hydrogen iodide (10034-85-2) + 13α-hydroxylupanine (15358-48-2) + red phosphorus → (+)-lupanine (550-90-3)

13α-hydroxylupanine (15358-48-2) + phosphorus pentoxide → water (7732-18-5) + (+)-lupanine (550-90-3)

Conditions	Yield
at 170℃; folgende Hydrierung;

6β-hydroxylupanine → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: CHCl3 / 12 h / Ambient temperature 2: 3.2 mg / H2 / 5percent Pd-C / ethanol View Scheme

O,O'-dibenzoyl-D-tartaric acid (17026-42-5) + rac-lupanine (4356-43-8) → (-)-lupanine (+)-2,3-dibenzoyl-D-tartarate (1335287-92-7) + (+)-lupanine (550-90-3) + L-(-)-lupanine (486-88-4)

Conditions	Yield
In methanol Resolution of racemate; Heating; optical yield given as %ee;

L-Tartaric acid (87-69-4) + rac-lupanine (4356-43-8) → (+)-lupanine (550-90-3)

Conditions	Yield
Stage #1: L-Tartaric acid; rac-lupanine In acetone Resolution of racemate; Stage #2: With potassium hydroxide In water Resolution of racemate;	n/a

6-methyl-3,7-diazabicyclo[3.3.1]non-6-en-2-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: triethylamine; dmap / dichloromethane / 20 h 2.1: triethylamine / tetrahydrofuran / 5 h / 20 °C 3.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 4.1: sodium tetrahydroborate / 2.5 h / 0 °C 4.2: 4 h / 0 - 20 °C 5.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 6.1: triethylamine / dichloromethane / 120 h 7.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 8.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

3-tert-butoxycarbonyl-6-methyl-3,7-diazabicyclo[3.3.1]non-6-en-2-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: triethylamine / tetrahydrofuran / 5 h / 20 °C 2.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 3.1: sodium tetrahydroborate / 2.5 h / 0 °C 3.2: 4 h / 0 - 20 °C 4.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 5.1: triethylamine / dichloromethane / 120 h 6.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 7.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

11-tert-butoxycarbonyl-7,11-diazatricyclo[7.3.1.02,7]tridec-2,4-dien-6,10-dione → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 2.1: sodium tetrahydroborate / 2.5 h / 0 °C 2.2: 4 h / 0 - 20 °C 3.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 4.1: triethylamine / dichloromethane / 120 h 5.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 6.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S)-11-tert-butoxycarbonyl-7,11-diazatricyclo[7.3.1.02,7]tridecane-6,10-dione → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: sodium tetrahydroborate / 2.5 h / 0 °C 1.2: 4 h / 0 - 20 °C 2.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 3.1: triethylamine / dichloromethane / 120 h 4.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 5.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S)-11-tert-butoxycarbonyl-10-methoxy-7,11-diazatricyclo[7.3.1.02,7]tridecane-6-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 4 steps 1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 2: triethylamine / dichloromethane / 120 h 3: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 4: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(-)-Angustifoline (550-43-6) → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 120 h 2: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 3: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S,10S)-10,11-diallyl-7,11-diazatricyclo[7.3.1.02,7]tridecane-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 2: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(+)-lupanine (550-90-3) → lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 48h;	90%

(+)-lupanine (550-90-3) → (-)-sparteine (90-39-1)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran Heating;	85%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 18h; Reflux;	84%
With hydrogenchloride; platinum Hydrogenation;
With lithium aluminium tetrahydride In diethyl ether for 5h; Heating;

(+)-lupanine (550-90-3) → (+)-lupanine N-oxide

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane	80%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 6h; Ambient temperature;	71%

bromocyane (506-68-3) + (+)-lupanine (550-90-3) → (1S)-4c-(4-bromo-butyl)-8-oxo-(11ac)-octahydro-1r,5c-methano-pyrido[1,2-a][1,5]diazocine-3-carbonitrile (2584-20-5)

Conditions	Yield
With benzene

(+)-lupanine (550-90-3) + methyl iodide (74-88-4) → N-16-methyl-2-oxosparteine iodide (6080-95-1, 54815-53-1, 58846-15-4, 82978-45-8, 82978-46-9, 115113-81-0)

Conditions	Yield
at 110 - 120℃; im Rohr;
for 96h; Ambient temperature; Yield given;

(+)-lupanine (550-90-3) → (+)-2-Thionosparteine

Conditions	Yield
With tetraphosphorus decasulfide; potassium polysulfide; xylene

(+)-lupanine (550-90-3) → 17-hydroxylupanine (15043-17-1, 55732-48-4, 69427-33-4, 127515-92-8)

Conditions	Yield
With N-Bromosuccinimide; chloroform und anschliessenden Behandeln mit wss.NaOH;
With methanol; silver(l) oxide
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,4-dioxane

(+)-lupanine (550-90-3) → (7S)-3,3-dichloro-(7at,14ac)-dodecahydro-7r,14c-methano-dipyrido[1,2-a;1',2'-e][1,5]diazocin-4-one

Conditions	Yield
With phosphorus pentachloride anschliessend Behandeln mit Eis;

(+)-lupanine (550-90-3) → (+)-2,17-dioxosparteine (4697-83-0)

Conditions	Yield
With potassium permanganate; acetic acid; acetone
With sodium hydroxide; potassium hexacyanoferrate(III)

(+)-lupanine (550-90-3) → 4-((1S)-(11at)-decahydro-1r,5c-methano-pyrido[1,2-a][1,5]diazocin-4t-yl)-butyric acid ; dihydrochloride (15333-74-1, 33964-84-0, 117895-46-2)

Conditions	Yield
With hydrogenchloride
With hydrogenchloride

iodomethane-d3 (865-50-9) + (+)-lupanine (550-90-3) → C16H24(2)H3N2O(1+)*I(1-)

Conditions	Yield
In acetone for 72h;

(+)-lupanine (550-90-3) → (+)-2,17-dioxosparteine (4697-83-0, 38485-03-9)

Conditions	Yield
With potassium permanganate

(+)-lupanine (550-90-3) → (2,2-2H2)sparteine (19879-75-5, 20210-08-6, 20210-10-0)

Conditions	Yield
With lithium aluminium deuteride In tetrahydrofuran for 1h; Heating;	50 mg

benzyl bromide (100-39-0) + (+)-lupanine (550-90-3) → (+)-lupanine-bromobenzylate

ethyl iodide (75-03-6) + (+)-lupanine (550-90-3) → (+)-lupanine hydriodide

ethanol (64-17-5) + ethyl iodide (75-03-6) + (+)-lupanine (550-90-3) → (+)-lupanine hydriodide

benzyl chloride (100-44-7) + (+)-lupanine (550-90-3) → (+)-lupanine hydrochloride

(+)-lupanine (550-90-3) + methyl iodide (74-88-4) → (+)-lupanine iodomethylate

Upstream product

• 3019-47-4 lupanine N⁽¹⁶⁾-oxide 
• 17026-42-5 O,O'-dibenzoyl-D-tartaric acid 
• 4356-43-8 rac-lupanine 
• 87-69-4 L-Tartaric acid 
• 550-43-6 (-)-Angustifoline 
• 1476-39-7 1,5-diaminopentane dihydrochloride 
• 90-39-1 (-)-sparteine 
• 15358-48-2 13α-hydroxylupanine 
• 10034-85-2 hydrogen iodide 
• 32101-29-4 5,6-dehydrolupanine 

Downstream Products

• 15043-17-1 17-hydroxylupanine 
• 4697-83-0 (+)-17-oxolupanine 
• 90-39-1 (-)-sparteine 
• 4697-83-0 (+)-2,17-dioxosparteine 
• 106656-92-2 2-(p-tolyl)-2-dehydrosparteine 
• 67528-17-0 (+)-2,3-Didehydrospartein 

Relevant academic research and scientific papers

LUPIN ALKALOIDS FROM THE SEEDS OF THERMOPSIS LUPINOIDES

A new lupin alkaloid (+)-lupanine N-oxide, was isolated from the seeds of Thermopsis lupinoides together with nine known alkaloids.The structure of the new compound was determined by spectroscopic methods and chemical transformations.

ALKALOIDS OF BOLUSANTHUS SPECIOSUS

Investigation of the alkaloids of Bolusanthus speciosus afforded a new quinolizidine alkaloid, 6β-hydroxylupanine.The structure of this alkaloid was assigned on the basis of spectroscopic methods and by chemical transformations.The other alkaloids isolated were cytisine, N-methylcytisine, 11α-allylcytisine, anagyrine, 13-hydroxyanagyrine, 5,6-dehydrolupanine, lupanine, sparteine and β-isoparteine.The biosynthetic significance of these finding is discussed briefly. Key Word Index - Bolusanthus speciosus; Leguminosae; ten quinolizidine alkaloids; novel 6β-hydroxylupanine.

The Enantioselective Total Synthesis of Bisquinolizidine Alkaloids: A Modular “Inside-Out” Approach

Bisquinolizidine alkaloids are characterized by a chiral bispidine core (3,7-diazabicyclo[3.3.1]nonane) to which combinations of an α,N-fused 2-pyridone, an endo- or exo-α,N-annulated piperidin(on)e, and an exo-allyl substituent are attached. We developed a modular “inside-out” approach that permits access to most members of this class. Its applicability was proven in the asymmetric synthesis of 21 natural bisquinolizidine alkaloids, among them more than ten first enantioselective total syntheses. Key steps are the first successful preparation of both enantiomers of C2-symmetric 2,6-dioxobispidine by desymmetrization of a 2,4,6,8-tetraoxo precursor, the construction of the α,N-fused 2-pyridone by using an enamine-bromoacrylic acid strategy, and the installation of endo- or, optionally, exo-annulated piperidin(on)es.

PROCESS FOR CONVERTING LUPANINE INTO SPARTEINE

The present invention relates to processes for preparing enantiopure Lupanine and Sparteine.

Process for preparing enantiopure Lupanine and Sparteine

The present invention relates to processes for preparing enantiopure Lupanine and Sparteine.

Simple and highly efficient preparation and characterization of (-)-lupanine and (+)-sparteine

In a simple and convenient way, we have improved the non-chromatographic isolation of optically pure (-)-2-oxosparteine ((-)-lupanine) and (+)-sparteine. The fast and efficient method for the determination of the ee of bisquinolizidine alkaloids has been proposed. A relatively simple simple 1H NMR method has been applied for evaluation of the % ee of enantiomers of the lupanines and sparteines with the chiral dibenzoyltartaric acids as the shift reagents. The 1H NMR spectra of the bases and the new salts in polar solvents have been measured. The results are confirmed by chiral HPLC method. Additionally, for the first time X-ray analysis of the salt of (-)-lupanine has been performed. The improved method of purification of bisquinolizidine alkaloids will considerably facilitate the employment of these alkaloids as chiral ligands in asymmetric reactions and as pharmacological tools.

ABSOLUTE CONFIGURATION OF (+)-5,6-DEHYDROLUPANINE, A KEY INTERMEDIATE IN BIOSYNTHESIS OF LUPIN ALKALOIDS

(+)-5,6-Dehydrolupanine, a key intermediate in biosynthesis of lupin alkaloids, was isolated from Thermopsis chinensis.The absolute configuration of the compound was determined to be 7R,9R,11R by chemical transformation to (-)-lupanine.Key Word Index - Thermopsis chinensis; Leguminosae; aerial parts; lupin alkaloid; quinolizidine alkaloid; (+)-5,6-dehydrolupanine; lupanine; absolute configuration; biosynthesis.

Synthesis of Cadaverine and its Incorporation into five Quinolizidine Alkaloids

Cadaverine dihydrochloride (13) was synthesised by the sequential introduction of two equivalents of sodium cyanide to a C3 precursor, and it was fed to Lupinus luteus and L. polyphyllus plants.Complete labelling patterns were obtained in five quinolizidine alkaloids by 13C n.m.r. spectroscopy.The 13C-13C doublets observed in the spectra of (-)-lupinine (3), (-)-sparteine (4), (+)-lupanine (5), (+)-13α-hydroxylupanine (6), and (+)-angustifoline (7) derived biosynthetically from the doubly labelled precursor (13) confirm the intact, specific incorporation of two cadaverine units into the tetracyclic quinolizidine alkaloid skeletons.The cadaverine (13) units are incorporated to about the same extent into each part of the quinolizidine alkaloids (3)-(7).Two of the 13C chemical shifts for lupanine (5) have been reassigned.The labelling pattern of the tricyclic alkaloid angustifoline (7) indicates that the allyl group originates by degradation of one ring of a tetracyclic precursor.

Lactams of sparteine

(2,2-2H2)Sparteine, (6-2H)sparteine, (10,10-2H2)sparteine, (15,15-2H2)sparteine, (17α-2H)sparteine, (17β-2H)sparteine, (17,17-2H2)sparteine, (17α-2H)lupanine, and (17β-2H)lupanine were prepared and employed to assign the 1H nmr spectrum of sparteine.Contrary to a published report, photochemical oxidation of sparteine does not lead to 15-oxosparteine but to 17-oxosparteine.

LUPIN ALKALOIDS FROM ECHINOSOPHORA KOREENSIS

The nine known lupin alkaloids, (-)-cytisine, (-)-N-methylcytisine, (-)-N-(3-oxobutyl)cytisine, (-)-N-formylcytisine, (-)-rhombifoline, (-)-baptifoline, (-)-anagyrine.Lupanine and 5,6-5,6-dehydrolupanine, have been isolated from the freshly harvested leaves, stems and roots of Echinosophora koreensis.The seasonal variations in the alkaloid contents of this plant were also examined.Key Word Index-Echinosophora koreensis; Leguminosae; alkaloid; (-)-cytisine; (-)-N-methylcytisine; (-)-N-formylcytisine; (-)-N-(3-oxobutyl)-cytisine; lupanine; 5,6-dehydrolupanine; (-)-anigyrine; seasonal variation in alkaloid content.