(2S,3S,4S,5R,6R)-Methyl 6-((1R,2S,3R,4R,5R)-3-acetoxy-4-azido-6,8-dioxabicyclo[3,2,1]octan-2-yloxy)-4,5-bis(benzyloxy)-3-(chlorocarbonyloxy)tetrahydro-2H-pyran-2-carboxylate

Base Information

• Chemical Name: (2S,3S,4S,5R,6R)-Methyl 6-((1R,2S,3R,4R,5R)-3-acetoxy-4-azido-6,8-dioxabicyclo[3,2,1]octan-2-yloxy)-4,5-bis(benzyloxy)-3-(chlorocarbonyloxy)tetrahydro-2H-pyran-2-carboxylate
• CAS No.: 87907-02-6
• Molecular Formula: C31H34ClN3O12
• Molecular Weight: 676.077
• Mol file: 87907-02-6.mol

Synonyms:O-(Methyl 2,3-di-o-benzyl-4-chloroacetyl-beta-D-glucopyranosyluronate)-(1-4)-3-0-acetyl-1,6-anhydro-2-azide-2-deoxy-beta-D-glucopyranose; O-[methyl2,3-di-O-benzyl-4-O-chloroacetyl-beta-Dglucopyranosyluronate]-( 1-4)-3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-beta-D-glucopyranose

Chemical Property of (2S,3S,4S,5R,6R)-Methyl 6-((1R,2S,3R,4R,5R)-3-acetoxy-4-azido-6,8-dioxabicyclo[3,2,1]octan-2-yloxy)-4,5-bis(benzyloxy)-3-(chlorocarbonyloxy)tetrahydro-2H-pyran-2-carboxylate

Chemical Property:

• PSA: 184.03000
• LogP: 2.40936

Purity/Quality:

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

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

SDS file from LookChem

Useful:

Technology Process of (2S,3S,4S,5R,6R)-Methyl 6-((1R,2S,3R,4R,5R)-3-acetoxy-4-azido-6,8-dioxabicyclo[3,2,1]octan-2-yloxy)-4,5-bis(benzyloxy)-3-(chlorocarbonyloxy)tetrahydro-2H-pyran-2-carboxylate

There total 48 articles about (2S,3S,4S,5R,6R)-Methyl 6-((1R,2S,3R,4R,5R)-3-acetoxy-4-azido-6,8-dioxabicyclo[3,2,1]octan-2-yloxy)-4,5-bis(benzyloxy)-3-(chlorocarbonyloxy)tetrahydro-2H-pyran-2-carboxylate 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: 50.0%

3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose (87326-68-9) + methyl (2,3-di-O-benzyl-4-O-chloroacetyl-α-D-glucopyranosyl bromide)uronate (87907-01-5) → O-(methyl 2,3-di-O-benzyl-4-O-(chloroacetyl)-β-D-glucopyranosyluronate)-(1->4)-3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose (87907-02-6)

Guidance literature:

With silver (II) carbonate; 4 A molecular sieve; In dichloromethane; for 144h; Ambient temperature;

DOI:10.1016/0008-6215(84)85236-2

Reference yield:

p-methylphenyl 2,3-di-O-benzyl-4,6-O-(R)-benzylidene-1-thio-β-D-glucopyranoside (850416-39-6) → O-(methyl 2,3-di-O-benzyl-4-O-(chloroacetyl)-β-D-glucopyranosyluronate)-(1->4)-3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose (87907-02-6) + O-(methyl 2,3-di-O-benzyl-4-O-chloroacetyl-α-D-glucopyranosyluronate)-(1→4)-2-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose

Guidance literature:

Multi-step reaction with 6 steps

1.1: trifluoroacetic acid / dichloromethane; water / 0.33 h / 20 °C

2.1: 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene / dichloromethane; water / 5 h / 20 °C

3.1: potassium hydrogencarbonate / N,N-dimethyl-formamide / 4 h / 0 - 20 °C

4.1: pyridine / dichloromethane / 6 h / 0 - 20 °C

5.1: iodine(I) bromide / dichloromethane / 4 h / 20 °C

6.1: dichloromethane / 0.5 h / 20 °C / Molecular sieve; Inert atmosphere

6.2: 96 h / 20 °C / Molecular sieve; Inert atmosphere

With pyridine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene; iodine(I) bromide; potassium hydrogencarbonate; trifluoroacetic acid; In dichloromethane; water; N,N-dimethyl-formamide;

DOI:10.1002/cmdc.201400019

Reference yield:

D-Glucose (2280-44-6) → O-(methyl 2,3-di-O-benzyl-4-O-(chloroacetyl)-β-D-glucopyranosyluronate)-(1->4)-3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose (87907-02-6)

Guidance literature:

Multi-step reaction with 13 steps

1.1: hydrogenchloride / 5 h / 0 - 75 °C / Industry scale

2.1: toluene-4-sulfonic acid / N,N-dimethyl-formamide / 2 h / 100 - 105 °C / Vacuum; Industry scale

3.1: sodium hydroxide / tetrabutylammomium bromide / toluene; 1-methyl-pyrrolidin-2-one / 20 °C / Industry scale

4.1: toluene-4-sulfonic acid; water / methanol / 70 - 75 °C / Industry scale

5.1: pyridine / 80 - 85 °C

5.2: 55 - 60 °C / Industry scale

6.1: water; acetic acid / dichloromethane / 40 - 45 °C / Industry scale

7.1: Jones reagent / acetone / 40 - 45 °C / Industry scale

8.1: potassium tert-butylate / dimethyl sulfoxide / 95 - 122 °C

8.2: pH 2 - 2.5

9.1: potassium carbonate / acetone / 2 h / 30 - 40 °C

10.1: pyridine / dichloromethane / 0 - 10 °C / Industry scale

11.1: water; mercury(II) oxide / water / 20 °C / Industry scale

11.2: Industry scale

12.1: triphenylphosphine; bromine / dichloromethane / 1 h / 20 °C

13.1: mercury dibromide / dichloromethane / 20 °C / Inert atmosphere; Molecular sieve

13.2: 20 °C / Inert atmosphere

With pyridine; Jones reagent; potassium tert-butylate; water; bromine; potassium carbonate; toluene-4-sulfonic acid; acetic acid; triphenylphosphine; mercury dibromide; mercury(II) oxide; sodium hydroxide; hydrogenchloride; tetrabutylammomium bromide; toluene-4-sulfonic acid; In 1-methyl-pyrrolidin-2-one; methanol; dichloromethane; water; dimethyl sulfoxide; N,N-dimethyl-formamide; acetone; toluene;

upstream raw materials:

diazomethane

(2S,3S,4S,5R,6R)-6-((1R,2S,3R,4R,5R)-3-Acetoxy-4-azido-6,8-dioxa-bicyclo[3.2.1]oct-2-yloxy)-4,5-bis-benzyloxy-3-(2-chloro-acetoxy)-tetrahydro-pyran-2-carboxylic acid

O-(2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranosyl)-(1->4)-1,6-anhydro-2,3-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-glucopyranose

3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose

Downstream raw materials:

O-(methyl 2,3-di-O-benzyl-β-D-glucopyranosyluronate)-(1->4)-3-O-acetyl-1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose

(2S,3S,4S,5R,6R)-6-((2R,3S,4R,5R)-4-Acetoxy-2-acetoxymethyl-5-azido-6-bromo-tetrahydro-pyran-3-yloxy)-4,5-bis-benzyloxy-3-(2-chloro-acetoxy)-tetrahydro-pyran-2-carboxylic acid methyl ester

O-(6-O-acetyl-2-azide-3,4-di-O-benzyl-2-deoxy-2-α-D-glucopyranosyl)-(1→4)-O-(methyl 2,3-di-O-benzyl-β-D-glucopyranosyluronate)-(1→4)-3,6-di-O-acetyl-2-azido-2-deoxy-β-D-glucopyranosyl trichloroacetimidate

O-(6-O-acetyl-2-azide-3,4-di-O-benzyl-2-deoxy-2-α-D-glucopyranosyl)-(1→4)-O-(methyl 2,3-di-O-benzyl-β-D-glucopyranosyluronate)-(1→4)-3,6-di-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl trichloroacetimidate

Refernces

• 1、 -. "PROCESS FOR PREPARING HEPARINOIDS AND INTERMEDIATES USEFUL IN THE SYNTHESIS THEREOF". . . Retrieved 2013/02/28.
• 2、 Ichikawa,Ichikawa,Kuzuhara. "Synthesis, from cellobiose, of a trisaccharide closely related to the GlcNAc----GlcA----GlcN segment of the antithrombin-binding sequence of heparin.". . p. 273 - 282. Retrieved 2007/10/02.