Gelsemoxonine

Base Information

• Chemical Name: Gelsemoxonine
• CAS No.: 135626-64-1
• Molecular Formula: C4H10O3
• Molecular Weight: 106.1204
• Mol file: 135626-64-1.mol

Synonyms:gelsemoxonine;

Chemical Property of Gelsemoxonine

Chemical Property:

• PSA: 94.39000
• LogP: 1.46040

Purity/Quality:

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

SDS file from LookChem

Useful:

Technology Process of Gelsemoxonine

There total 20 articles about Gelsemoxonine 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:

benzyl ((1'S,2'S,3S,4'R,5'S,6'S)-1-methoxy-2-oxo-4'-propionyl-3',9'-dioxaspiro[indoline-3,8'-tricyclo[3.3.2.0(2,4)]decan]-6'-yl)carbamate (1341223-32-2) → Gelsemoxonine (135626-64-1)

Guidance literature:

benzyl ((1'S,2'S,3S,4'R,5'S,6'S)-1-methoxy-2-oxo-4'-propionyl-3',9'-dioxaspiro[indoline-3,8'-tricyclo[3.3.2.0(2,4)]decan]-6'-yl)carbamate; With trimethylsilyl iodide; In dichloromethane; at 0 ℃; for 1.5h; Inert atmosphere;

With sodium hydrogencarbonate; In dichloromethane; water;

DOI:10.1021/ja208617c

Reference yield:

((1S,6R,7R)-7-((E)-(1-methoxy-2-oxoindolin-3-ylidene)methyl)-5-oxo-3-oxabicyclo[4.1.0]heptan-7-yl)methyl pivalate (1341221-77-9) → Gelsemoxonine (135626-64-1)

Guidance literature:

Multi-step reaction with 16 steps

1.1: lithium hexamethyldisilazane / tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere

2.1: toluene / 2.33 h / 70 °C / Inert atmosphere

2.2: 20 °C / Inert atmosphere

3.1: sodium hydride / methanol; mineral oil / 0 - 20 °C / Inert atmosphere

4.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene / dichloromethane / 3 h / 20 °C

5.1: trimethylsilyl cyanide; 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 1 h / 0 °C / Inert atmosphere

5.2: 4 h / 0 °C / Inert atmosphere

6.1: pyrrolidine; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / acetonitrile / 3 h / 0 - 20 °C / Inert atmosphere

6.2: 20 °C

6.3: pH 1

7.1: oxalyl dichloride / dichloromethane / 1 h / 0 - 20 °C / Inert atmosphere

8.1: sodium azide / water; toluene / 0.17 h / 0 °C

9.1: toluene / 0.5 h / 80 °C / Inert atmosphere

10.1: toluene / 2 h / 70 °C / Inert atmosphere

11.1: oxalyl dichloride; N,N-dimethyl-formamide / 0 - 70 °C / Inert atmosphere

12.1: triethylsilane; tetrakis(triphenylphosphine) palladium⁽⁰⁾; triethylamine / N,N-dimethyl-formamide / 4.5 h / 80 °C / Inert atmosphere

13.1: tetrahydrofuran; diethyl ether / 1.75 h / -78 °C / Inert atmosphere

14.1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / dimethyl sulfoxide / 1.5 h / 20 - 50 °C

15.1: tert.-butylhydroperoxide; N-benzyl-trimethylammonium hydroxide / tetrahydrofuran; water / 1 h / -20 °C

16.1: trimethylsilyl iodide / dichloromethane / 1.5 h / 0 °C / Inert atmosphere

With pyrrolidine; triethylsilane; tert.-butylhydroperoxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium azide; oxalyl dichloride; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; trimethylsilyl iodide; trimethylsilyl cyanide; [bis(acetoxy)iodo]benzene; N-benzyl-trimethylammonium hydroxide; sodium hydride; 1,8-diazabicyclo[5.4.0]undec-7-ene; triethylamine; N,N-dimethyl-formamide; lithium hexamethyldisilazane; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In tetrahydrofuran; methanol; diethyl ether; dichloromethane; water; dimethyl sulfoxide; N,N-dimethyl-formamide; toluene; acetonitrile; mineral oil; 9.1: Curtius rearrangement;

DOI:10.1021/ja208617c

Reference yield:

C22H27NO7 → Gelsemoxonine (135626-64-1)

Guidance literature:

Multi-step reaction with 17 steps

1.1: N,N,N,N,-tetramethylethylenediamine; methanesulfonyl chloride / dichloromethane / 2.5 h / -78 °C / Inert atmosphere

2.1: lithium hexamethyldisilazane / tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere

3.1: toluene / 2.33 h / 70 °C / Inert atmosphere

3.2: 20 °C / Inert atmosphere

4.1: sodium hydride / methanol; mineral oil / 0 - 20 °C / Inert atmosphere

5.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene / dichloromethane / 3 h / 20 °C

6.1: trimethylsilyl cyanide; 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 1 h / 0 °C / Inert atmosphere

6.2: 4 h / 0 °C / Inert atmosphere

7.1: pyrrolidine; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / acetonitrile / 3 h / 0 - 20 °C / Inert atmosphere

7.2: 20 °C

7.3: pH 1

8.1: oxalyl dichloride / dichloromethane / 1 h / 0 - 20 °C / Inert atmosphere

9.1: sodium azide / water; toluene / 0.17 h / 0 °C

10.1: toluene / 0.5 h / 80 °C / Inert atmosphere

11.1: toluene / 2 h / 70 °C / Inert atmosphere

12.1: oxalyl dichloride; N,N-dimethyl-formamide / 0 - 70 °C / Inert atmosphere

13.1: triethylsilane; tetrakis(triphenylphosphine) palladium⁽⁰⁾; triethylamine / N,N-dimethyl-formamide / 4.5 h / 80 °C / Inert atmosphere

14.1: tetrahydrofuran; diethyl ether / 1.75 h / -78 °C / Inert atmosphere

15.1: 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione / dimethyl sulfoxide / 1.5 h / 20 - 50 °C

16.1: tert.-butylhydroperoxide; N-benzyl-trimethylammonium hydroxide / tetrahydrofuran; water / 1 h / -20 °C

17.1: trimethylsilyl iodide / dichloromethane / 1.5 h / 0 °C / Inert atmosphere

With pyrrolidine; triethylsilane; tert.-butylhydroperoxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium azide; oxalyl dichloride; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; trimethylsilyl iodide; N,N,N,N,-tetramethylethylenediamine; trimethylsilyl cyanide; [bis(acetoxy)iodo]benzene; N-benzyl-trimethylammonium hydroxide; sodium hydride; methanesulfonyl chloride; 1,8-diazabicyclo[5.4.0]undec-7-ene; triethylamine; N,N-dimethyl-formamide; lithium hexamethyldisilazane; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In tetrahydrofuran; methanol; diethyl ether; dichloromethane; water; dimethyl sulfoxide; N,N-dimethyl-formamide; toluene; acetonitrile; mineral oil; 10.1: Curtius rearrangement;

DOI:10.1021/ja208617c

upstream raw materials:

((1S,6R,7R)-7-((E)-(1-methoxy-2-oxoindolin-3-ylidene)methyl)-5-oxo-3-oxabicyclo[4.1.0]heptan-7-yl)methyl pivalate

C₂₅H₃₃NO₆Si

((1S,3'S,5S)-1'-methoxy-2',9-dioxo-6-oxaspiro[bicyclo[3.2.2]non[2]ene-4,3'-indolin]-2-yl)methyl pivalate

(1S,3'S,5S)-2-(hydroxymethyl)-1'-methoxy-6-oxaspiro[bicyclo[3.2.2]non[2]ene-4,3'-indoline]-2',9-dione

Refernces

• 1、 Wang, Pingluan,Gao, Yang,Ma, Dawei. "Divergent Entry to Gelsedine-Type Alkaloids: Total Syntheses of (-)-Gelsedilam, (-)-Gelsenicine, (-)-Gelsedine, and (-)-Gelsemoxonine". . p. 11608 - 11612. Retrieved 2018.