(2'S,3S)-2'-ethenyl-4'-methylspiro[1H-indole-3,7'-9-oxa-4-azatetracyclo[6.3.1.02,6.05,11]dodecane]-2-one

Base Information

• Chemical Name: (2'S,3S)-2'-ethenyl-4'-methylspiro[1H-indole-3,7'-9-oxa-4-azatetracyclo[6.3.1.02,6.05,11]dodecane]-2-one
• CAS No.: 509-15-9
• Molecular Formula: C20H22 N2 O2
• Molecular Weight: 322.407
• European Community (EC) Number: 208-095-2
• Wikipedia: Gelsemine
• Mol file: 509-15-9.mol

Synonyms:gelsemin;gelsemine

Chemical Property of (2'S,3S)-2'-ethenyl-4'-methylspiro[1H-indole-3,7'-9-oxa-4-azatetracyclo[6.3.1.02,6.05,11]dodecane]-2-one

Chemical Property:

• Appearance/Colour: White powder
• Vapor Pressure: 7.08E-10mmHg at 25°C
• Melting Point: 181-183ºC
• Refractive Index: 1.5700 (estimate)
• Boiling Point: 493.4 °C at 760 mmHg
• PKA: 7.75 in 80% methylcellosolve
• Flash Point: 252.2 °C
• PSA: 41.57000
• Density: 1.33 g/cm³
• LogP: 2.10350
• Storage Temp.: 2-8°C
• XLogP3: 1.8
• Hydrogen Bond Donor Count: 1
• Hydrogen Bond Acceptor Count: 3
• Rotatable Bond Count: 1
• Exact Mass: 322.168127949
• Heavy Atom Count: 24
• Complexity: 635

Purity/Quality:

98%,99%, ^*data from raw suppliers

Gelsemine ^*data from reagent suppliers

Safty Information:

• Pictogram(s): A toxic plant alkaloid.
• Hazard Codes: T+
• Statements: 23/24/25-26/27/28
• Safety Statements: 36/37/39-45-28

MSDS Files:

SDS file from LookChem

Total 1 MSDS from other Authors

Useful:

• Canonical SMILES: CN1CC2(C3CC4C5(C2C1C3CO4)C6=CC=CC=C6NC5=O)C=C
• Isomeric SMILES: CN1C[C@]2(C3CC4[C@]5(C2C1C3CO4)C6=CC=CC=C6NC5=O)C=C
• Uses: Medicine, as a CNS stimulant

Technology Process of (2'S,3S)-2'-ethenyl-4'-methylspiro[1H-indole-3,7'-9-oxa-4-azatetracyclo[6.3.1.02,6.05,11]dodecane]-2-one

There total 33 articles about (2'S,3S)-2'-ethenyl-4'-methylspiro[1H-indole-3,7'-9-oxa-4-azatetracyclo[6.3.1.02,6.05,11]dodecane]-2-one which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield: 90.0%

21-oxogelsemine (55856-53-6) → gelsemine (509-15-9)

Guidance literature:

With diisobutylaluminium hydride; In toluene;

Reference yield:

(1R,2R,3S,4R,7R)-3-Chloro-7-hydroxy-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid methyl ester (321172-31-0) → gelsemine (509-15-9)

Guidance literature:

Multi-step reaction with 30 steps

1.1: 100 percent / tBuOOH; VO(acac)2 / benzene

2.1: 97 percent / 2,6-lutidine / CH₂Cl₂

3.1: 98 percent / tBuOK / benzene

4.1: methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) / toluene / -20 °C

5.1: piperidine / methanol

6.1: 87 percent / TBAF / tetrahydrofuran

7.1: CrO₃; H₂SO₄ / acetone

8.1: toluene; acetonitrile / 90 °C

9.1: nBuLi / tetrahydrofuran / 65 °C

10.1: tBuOK

11.1: 75 percent / nBu₃SnH; AIBN / benzene / Heating

12.1: 100 percent / methanol

13.1: 94 percent / pyridine; DMAP / CH₂Cl₂

14.1: 94 percent / LiBH₄; LiBEt₃H / tetrahydrofuran

15.1: pyrrolidine / [Pd(PPh₃)4] / tetrahydrofuran

16.1: DIEA / acetonitrile / 60 °C

17.1: 62 percent / KHMDS / tetrahydrofuran / -78 - 0 °C

18.1: 92 percent / pyridine; DMAP / CH₂Cl₂

19.1: 96 percent / HCO₂H

20.1: NEt₃ / tetrahydrofuran

21.1: NaBH₄; H₂O / tetrahydrofuran

22.1: PBu₃ / tetrahydrofuran

23.1: MCPBA / tetrahydrofuran

24.1: NEt₃ / tetrahydrofuran

25.1: MCPBA / tetrahydrofuran; H₂O

26.1: NEt₃ / tetrahydrofuran

27.1: 96 percent / K₂CO₃; MeOH

28.1: Hg(OTf)2*PhNMe₂ / nitromethane

28.2: aq. NaCl

28.3: NaBH₄; aq. NaOH; BnNEt₃Cl / CH₂Cl₂

29.1: TMSCl; NaI / acetonitrile

29.2: 63 percent / NEt₃ / methanol

30.1: 90 percent / DIBAL / toluene

With pyrrolidine; piperidine; pyridine; 2,6-dimethylpyridine; chromium(VI) oxide; methanol; tert.-butylhydroperoxide; dmap; sodium tetrahydroborate; lithium borohydride; n-butyllithium; chloro-trimethyl-silane; formic acid; bis(acetylacetonate)oxovanadium; 2,2'-azobis(isobutyronitrile); tributylphosphine; Hg(OSO₂CF₃)2*C₆H₅N(CH₃)2; sulfuric acid; potassium tert-butylate; tetrabutyl ammonium fluoride; water; tri-n-butyl-tin hydride; potassium hexamethylsilazane; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum; diisobutylaluminium hydride; lithium triethylborohydride; potassium carbonate; triethylamine; N-ethyl-N,N-diisopropylamine; 3-chloro-benzenecarboperoxoic acid; sodium iodide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; In tetrahydrofuran; methanol; nitromethane; dichloromethane; water; acetone; toluene; acetonitrile; benzene; 7.1: Jones' oxidation / 9.1: Horner-Emmons reaction / 12.1: Michael addition / 17.1: Michael addition;

Reference yield:

(1R,2R,3R,4R,7R)-3-Chloro-7-dimethylsilanyl-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid methyl ester (321172-27-4) → gelsemine (509-15-9)

Guidance literature:

Multi-step reaction with 31 steps

1.1: 53 percent / aq. H₂O₂; KF; KHCO₃ / tetrahydrofuran; methanol

2.1: 100 percent / tBuOOH; VO(acac)2 / benzene

3.1: 97 percent / 2,6-lutidine / CH₂Cl₂

4.1: 98 percent / tBuOK / benzene

5.1: methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) / toluene / -20 °C

6.1: piperidine / methanol

7.1: 87 percent / TBAF / tetrahydrofuran

8.1: CrO₃; H₂SO₄ / acetone

9.1: toluene; acetonitrile / 90 °C

10.1: nBuLi / tetrahydrofuran / 65 °C

11.1: tBuOK

12.1: 75 percent / nBu₃SnH; AIBN / benzene / Heating

13.1: 100 percent / methanol

14.1: 94 percent / pyridine; DMAP / CH₂Cl₂

15.1: 94 percent / LiBH₄; LiBEt₃H / tetrahydrofuran

16.1: pyrrolidine / [Pd(PPh₃)4] / tetrahydrofuran

17.1: DIEA / acetonitrile / 60 °C

18.1: 62 percent / KHMDS / tetrahydrofuran / -78 - 0 °C

19.1: 92 percent / pyridine; DMAP / CH₂Cl₂

20.1: 96 percent / HCO₂H

21.1: NEt₃ / tetrahydrofuran

22.1: NaBH₄; H₂O / tetrahydrofuran

23.1: PBu₃ / tetrahydrofuran

24.1: MCPBA / tetrahydrofuran

25.1: NEt₃ / tetrahydrofuran

26.1: MCPBA / tetrahydrofuran; H₂O

27.1: NEt₃ / tetrahydrofuran

28.1: 96 percent / K₂CO₃; MeOH

29.1: Hg(OTf)2*PhNMe₂ / nitromethane

29.2: aq. NaCl

29.3: NaBH₄; aq. NaOH; BnNEt₃Cl / CH₂Cl₂

30.1: TMSCl; NaI / acetonitrile

30.2: 63 percent / NEt₃ / methanol

31.1: 90 percent / DIBAL / toluene

With pyrrolidine; piperidine; pyridine; 2,6-dimethylpyridine; chromium(VI) oxide; methanol; tert.-butylhydroperoxide; dmap; potassium fluoride; sodium tetrahydroborate; lithium borohydride; n-butyllithium; chloro-trimethyl-silane; formic acid; bis(acetylacetonate)oxovanadium; 2,2'-azobis(isobutyronitrile); tributylphosphine; Hg(OSO₂CF₃)2*C₆H₅N(CH₃)2; sulfuric acid; potassium tert-butylate; tetrabutyl ammonium fluoride; water; dihydrogen peroxide; tri-n-butyl-tin hydride; potassium hexamethylsilazane; bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminum; diisobutylaluminium hydride; lithium triethylborohydride; potassium carbonate; potassium hydrogencarbonate; triethylamine; N-ethyl-N,N-diisopropylamine; 3-chloro-benzenecarboperoxoic acid; sodium iodide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; In tetrahydrofuran; methanol; nitromethane; dichloromethane; water; acetone; toluene; acetonitrile; benzene; 8.1: Jones' oxidation / 10.1: Horner-Emmons reaction / 13.1: Michael addition / 18.1: Michael addition;

upstream raw materials:

21-oxogelsemine

(1R,2R,3S,4R,7R)-3-Chloro-7-hydroxy-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid methyl ester

(1R,2R,3R,4R,7R)-3-Chloro-7-dimethylsilanyl-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid methyl ester

(1S,2R,4S,5R,6R,7S,8R)-7-Chloro-8-hydroxy-3-oxa-tricyclo[3.2.1.0^2,4]octane-6-carboxylic acid methyl ester

Downstream raw materials:

18,19-dihydro-gelsemine

Dihydrogelsemin

Refernces

• 1、 Yokoshima, Satoshi,Tokuyama, Hidetoshi,Fukuyama, Tohru. "Enantioselective Total Synthesis of (+)-Gelsemine: Determination of Its Absolute Configuration". . p. 4073 - 4075. Retrieved 2007/10/03.