Triphenylphosphine → HCID 86757014, compound

HRID 1067108Notes

Reaction equation

HRID 1067108 reaction equation
[C:1]([NH:8][C@H:9]([C:18]([N:20]([CH3:35])[C@H:21]([CH2:33][OH:34])[CH2:22][CH2:23][CH2:24][NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])=[O:19])[CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[SH:36][C:37]1[S:38][C:39]2[CH:45]=[CH:44][CH:43]=[CH:42][C:40]=2[N:41]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[S:38]1[C:39]2[CH:45]=[CH:44][CH:43]=[CH:42][C:40]=2[N:41]=[C:37]1[S:36][C:33](=[O:34])[C@H:21]([CH2:22][CH2:23][CH2:24][NH:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[N:20]([C:18](=[O:19])[C@H:9]([CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[NH:8][C:1]([O:3][C:4]([CH3:6])([CH3:5])[CH3:7])=[O:2])[CH3:35]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 86757015HCID 86757015, compoundHCID 178418395HCID 178418395, compound

Product 1

HCID 86757014HCID 86757014, compoundYield 51.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

This was prepared in a two step sequence. A solution of Boc-homophenylalanyl-Nδ-Boc-Nα-methylornithinol (D) (392 mg) and 2-mercaptobenzothiazole (267 mg) in dry tetrahydrofuran (9 ml) was cooled to 0° C. under nitrogen atmosphere. Then, a solution of triphenylphosphine (1.04 g), anhydrous tetrahydrofuran (1 ml), and diethyl azodicarboxylate (620 μl) was added. The reaction mixture was stirred for 1.5 h at 0° C., concentrated in vacuo, and purified by flash chromatography (30% ethyl acetate/hexane) to give Boc-homophenylalanyl-Nδ-Boc-Nα-methylornithinyl 2-benzo-thiazolyl thioether (270 mg). This intermediate was deprotected by Procedure E to afford titled product (75 mg): HPLC [20 to 40% gradient (acetonitrile/0.1% TFA) over 60 min, retention time=42.96 min]; 1H NMR (400 MHz, D2O) δ1.49 (m, 2H), 1.83 (m, 2H), 1.98 (m, 1H), 2.18 (m, 1H), 2.79 (m, 2H), 2.82 (s, 3H), 3.09 (m, 2H), 3.57 (dd, J=14.8; 11.2 Hz, 1H), 3.70 (dd, J=14.8; 4.0 Hz, 1H), 4.46 (m, 1H), 5.01 (m, 1H), 7.17 (m, 2H), 7.38 (m, 3H), 7.49 (t, J=8.0 Hz, 1H), 7.61 (t, J=7.2 Hz, 1H), 7.91 (d, J=8.0 Hz, 1H), and 7.94 (d, J=8.4 Hz, 1H).

Workup

  1. customThis was prepared in a two step sequence
  2. concentrationconcentrated in vacuo
  3. custompurified by flash chromatography (30% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-2d6c0814b5374229ba170a7782ffe246
Source dataset
uspto-grants-2001_06
Patent number
US06245746B1

Reaction notes

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