tert-Butyl hydroperoxide → Phenyl-3-(N-carbobenzyloxyvalyl)amino-4-phenylbut-2-enyl Sulfone

HRID 2111542Notes

Reaction equation

HRID 2111542 reaction equation
[C:1]1([CH:7]([C:66]2[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=2)[C@H:8]([NH:48][C:49](=[O:65])[C@H:50]([CH:62]([CH3:64])[CH3:63])[NH:51][C:52]([O:54][CH2:55][C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)=[O:53])[CH:9]=[CH:10][S:11]([CH:14]=[CH:15][C@@H:16]([NH:30][C:31](=[O:47])[C@H:32]([CH:44]([CH3:46])[CH3:45])[NH:33][C:34]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:35])[CH:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:13])=[O:12])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.C(OO)(C)(C)C.C1(C(C2C=CC=CC=2)[C@H](NC(=O)[C@H](CC(C)C)NC(OCC2C=CC=CC=2)=O)C=CS(C=C[C@@H](NC(=O)[C@H](CC(C)C)NC(OCC2C=CC=CC=2)=O)C(C2C=CC=CC=2)C2C=CC=CC=2)(=O)=O)C=CC=CC=1>C1COCC1>[C:18]1([CH:17]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:16]([NH:30][C:31](=[O:47])[C@H:32]([CH:44]([CH3:45])[CH3:46])[NH:33][C:34]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:35])=[CH:15][CH2:14][S:11]([CH2:10][CH:9]=[C:8]([NH:48][C:49](=[O:65])[C@H:50]([CH:62]([CH3:64])[CH3:63])[NH:51][C:52]([O:54][CH2:55][C:56]2[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=2)=[O:53])[CH:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:66]2[CH:67]=[CH:68][CH:69]=[CH:70][CH:71]=2)(=[O:12])=[O:13])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 86608592HCID 86608592, compoundHCID 86608595HCID 86608595, compoundHCID 178418339Butyllithium

Product 1

HCID 86608594Phenyl-3-(N-carbobenzyloxyvalyl)amino-4-phenylbut-2-enyl SulfoneYield 21%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Cbz-Val-Phe-VS-Ph was treated with butyllithium and tert-butylhydroperoxide in freshly distilled THF as described with Cbz-Leu-Phe-VS-Ph above to give Cbz-Val-Phe-AS-Ph as a white powder, yield 21%. 1H-NMR (CDCl3) δ 0.70-0.85 (2d, 6H, Val-CH3), 2.1 (m, 1H, Val-CH), 3.80 (d, 2H, CH2-Phe), 3.95 (m, 3H, CH2—SO2 and α-H), 4.90 (t, 1H, CH═), 5.12 (m, 3H, NH and Cbz), 7.1-7.4 (m, 10H, 2×Ph), 7.55 (t, 2H, SO2-Ph), 7.65 (t, 1H, SO2-Ph), 7.91 (d, 2H, SO2-Ph), 8.42 (b, 1H, NH). 13C NMR (300 MHz, CDCl3) δ 172.1, 156.3, 144.4, 140.8, 135.7, 134.2, 133.6, 131.2, 129.5, 129.4×2, 129.3, 128.8×2, 128.7, 128.6, 128.4, 128.3, 127.8, 127.3, 126.9, 106.3, 67.6, 56.0, 55.6, 41.7, 22.0, 21.0, 18.4. MS (FAB+) m/z 521 (M+1, 100%). Anal. calcd. for C29H32N2O5S.1/10 H2O: C, 66.67; H, 6.21; N, 5.36. Found: C, 66.31; H, 6.23; N, 5.26.

Sources & evidence

ORD record
ord-b2e3da911ea348368853122b9b5b525f
Source dataset
uspto-grants-2009_04
Patent number
US07521427B2

Reaction notes

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