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Phenol → HCID 68637794, compound

HRID 2357131
Notes
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Reaction equation

HRID 2357131 reaction equation
C1(O)C=CC=CC=1.[C:8]([O:12][C:13](=[O:39])[CH2:14][N:15]([C:24]1[CH:29]=[CH:28][C:27](Br)=[CH:26][C:25]=1[O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH2:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])([CH3:11])([CH3:10])[CH3:9].C(OC(C(NC1C=CC([C:67]2([OH:97])[C:80]3[CH:79]=[C:78]([F:81])[C:77]([O:82][CH2:83][O:84][CH2:85][CH2:86][O:87][CH3:88])=[CH:76][C:75]=3[O:74][C:73]3[C:68]2=[CH:69][C:70]([F:96])=[C:71]([O:89][CH2:90][O:91][CH2:92][CH2:93][O:94][CH3:95])[CH:72]=3)=CC=1OCC(O)=O)C(OC(C)(C)C)=O)=O)(C)(C)C.NC1C=CC=CC=1O.N(CC(O)=O)CC(O)=O>>[C:8]([O:12][C:13](=[O:39])[CH2:14][N:15]([C:24]1[CH:29]=[CH:28][C:27]([C:67]2([OH:97])[C:68]3[CH:69]=[C:70]([F:96])[C:71]([O:89][CH2:90][O:91][CH2:92][CH2:93][O:94][CH3:95])=[CH:72][C:73]=3[O:74][C:75]3[C:80]2=[CH:79][C:78]([F:81])=[C:77]([O:82][CH2:83][O:84][CH2:85][CH2:86][O:87][CH3:88])[CH:76]=3)=[CH:26][C:25]=1[O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH2:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])([CH3:11])([CH3:10])[CH3:9]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 5

HCID 996PhenolHCID 58012-AminophenolHCID 8897Iminodiacetic acidHCID 68637071{2-(Bis-tert-butoxycarbonylmethyl-amino)-5-[2,7-difluoro-9-hydroxy 3,6-bis-(2-methoxy-ethoxymethoxy)-9H-xanthen-9-yl]-phenoxy}-acetic acidHCID 90684652[(2-Benzyloxy-4-bromo-phenyl)-tert-butoxycarbonylmethyl-amino]-acetic acid tert-butyl ester3×

Product 1

HCID 68637794HCID 68637794, compoundYield 69%

Procedure

The synthesis of the fluorescein precursor compound 18 is shown in Scheme 5. The xanthene half of 18 was synthesized from the xanthone precursor 7. The latter was prepared via the Friedel-Crafts acylation of 342 with 6. The product was subsequently heated in a sealed tube to furnish the xanthone 8 and the phenol moieties then protected as 2-methoxyethoxymethyl (MEM)43 ethers (9). The aromatic precursor (13) to the “northern” half of compound 18 was prepared in three steps from commercially available o-aminophenol (described above). Compound 13 contains a doubly protected iminodiacetic acid moiety and a benzylated phenol. The latter will ultimately be debenzylated so that it can serve as the attachment site for the peptide. Compound 13 was lithiated at −105° C. and coupled to 9, to furnish adduct 14 in 69% yield. The benzylated phenol in 14 was transformed in three steps to the desired carboxylic acid (18), and then coupled to H2N-Ser(O-tBu)-Phe-[(Arg)Mtr]4-resin (prepared via standard Fmoc solid phase peptide synthesis on the Rink resin). Finally, exposure of the resin-appended fluorophore-peptide to 95% CF3CO2H resulted in the simultaneous cleavage of the peptide from the resin, MEM ether deprotection, and complete aromatization of the tricyclic nucleus via loss of the tertiary hydroxyl moiety to yield 23.

Workup

  1. customwas lithiated at −105° C.

Sources & evidence

ORD record
ord-ddc45e2227a64cef9124ed91ae923d59
Source dataset
uspto-grants-2010_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07759459B2

Reaction notes

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