Grahamimycin A(1)

Base Information

• Chemical Name: Grahamimycin A(1)
• CAS No.: 74838-13-4
• Molecular Formula: C₁₄H₁₈O₆
• Molecular Weight: 282.293
• Nikkaji Number: J1.210.128G
• Mol file: 74838-13-4.mol

Synonyms:grahamimycin A(1);grahamimycin A1

Chemical Property of Grahamimycin A(1)

Chemical Property:

• Vapor Pressure: 1.96E-11mmHg at 25°C
• Boiling Point: 532.9°C at 760 mmHg
• Flash Point: 239°C
• PSA: 86.74000
• Density: 1.13g/cm³
• LogP: 1.11820
• XLogP3: 0.6
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 6
• Rotatable Bond Count: 0
• Exact Mass: 282.11033829
• Heavy Atom Count: 20
• Complexity: 437

Purity/Quality:

Safty Information:

• Pictogram(s):  
• Hazard Codes: 

MSDS Files:

SDS file from LookChem

Useful:

• Canonical SMILES: CC1CC=CC(=O)OC(CC(=O)C(=O)CCC(=O)O1)C
• Isomeric SMILES: C[C@@H]1C/C=C\C(=O)O[C@@H](CC(=O)C(=O)CCC(=O)O1)C

Technology Process of Grahamimycin A(1)

There total 25 articles about Grahamimycin A(1) 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%

(E)-(6R,14R)-11,12-Dihydroxy-6,14-dimethyl-1,7-dioxa-cyclotetradec-3-ene-2,8-dione (82393-38-2,86194-95-8,86194-96-9,86194-97-0,116697-05-3,116697-06-4,133522-19-7) → (-)-grahamimycin A1 (74838-13-4)

Guidance literature:

With pyridinium trifluroacetate; dimethyl sulfoxide; dicyclohexyl-carbodiimide;

DOI:10.1016/S0040-4039(00)96920-X

Reference yield: 10.2%

(5R,14R)-6,14-dimethyl-4-(methylpropylsulfonio)-1,7-dioxacyclotetradec-11-yne-2,8-dione tetrafluoroborate → (-)-grahamimycin A1 (74838-13-4)

Guidance literature:

With pyridine; osmium(VIII) oxide; In tetrahydrofuran; for 0.25h;

DOI:10.1021/jo00204a009

Reference yield:

(Z)-(R)-7-(1-Ethoxy-ethoxy)-oct-4-enoic acid (116616-33-2) → (-)-grahamimycin A1 (74838-13-4)

Guidance literature:

Multi-step reaction with 7 steps

1: 82 percent / Dicyclohexylcarbodiimide (DCC) / N,N-Dimethyl-4-aminopyridine (DAMP)

2: 100 percent / HCl / H₂O; tetrahydrofuran

3: 97 percent

4: 1.) 0.1n HCl / 2.) pH=8.4

5: 95 percent / MCPBA

6: 88 percent / 20percent HClO₄

7: 50 percent / DMSO, DCC, Pyridiniumtrifluoracetat

With hydrogenchloride; perchloric acid; pyridinium trifluroacetate; dimethyl sulfoxide; 3-chloro-benzenecarboperoxoic acid; dicyclohexyl-carbodiimide; dmap; In tetrahydrofuran; water;

DOI:10.1016/S0040-4039(00)96920-X

upstream raw materials:

colletodiol

(E)-(6R,14R)-11,12-Dihydroxy-6,14-dimethyl-1,7-dioxa-cyclotetradec-3-ene-2,8-dione

(6R,12R,14R)-(3E,9E)-12-hydroxy-6,14-dimethyl-1,7-dioxacyclotetradeca-3,9-diene-2,8,11-trione

1-(tetrahydropyranyloxy)-4-pentyn

Downstream raw materials:

3-hydroxybutyric acid methyl ester

(2E)-5-Hydroxy-2-hexensaeuremethylester

Dimethyl succinate

(2E,4E)-methylhexa-2,4-dienoate

Refernces

Formal total synthesis of grahamimycin A₁

10.1016/S0040-4039(00)79484-6

The study presents the formal total synthesis of Grahamimycin A1, an unsymmetrical 14-membered macrocyclic dilactone antibiotic. Key chemicals involved include (S)-t-butyldimethylsiloxy-2-hexenoic acid and its (R)-isomer, which were prepared from (S)- and (R)-3-hydroxybutanoic acid esters respectively. These were condensed with 2-(p-toluenesulfonyl)ethyl (4S,5S,7R)-7-hydroxy-4,5-dimethylmethylenedoxyoctanoate, synthesized from methyl 4,6-dideoxy-α-D-xylo-hexopyranoside. The resulting esters were converted into precursors of seco acids of Grahamimycin A1 with S or R configuration at the C-6 position. The (6S)- and (6R)-isomers were subjected to macrolactonization using the diethyl azodicarboxylate-triphenylphosphine system or Yamaguchi procedure to afford 11,12-dihydroxy-Grahamimycin Al, whose oxidation to Grahamimycin A1 has been previously reported. The study highlights the use of protecting groups like t-butyldimethylsilyl (TBDMS) and 2-(p-toluenesulfonyl)ethyl (PTSE) groups to facilitate the synthesis and subsequent removal before macrolactonization.