N-Boc-Tyr(Bn)-Ala-Trp-OMe → N-Boc-Tyr-Ala-Trp-OMe

HRID 2074364Notes

Reaction equation

HRID 2074364 reaction equation
[NH:1]([C:41]([O:43][C:44]([CH3:47])([CH3:46])[CH3:45])=[O:42])[C@H:2]([C:18]([NH:20][C@H:21]([C:23]([NH:25][C@H:26]([C:37]([O:39][CH3:40])=[O:38])[CH2:27][C:28]1[C:36]2[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=2)[NH:30][CH:29]=1)=[O:24])[CH3:22])=[O:19])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([O:10]CC2C=CC=CC=2)=[CH:6][CH:5]=1>CO.[Pd]>[NH:1]([C:41]([O:43][C:44]([CH3:45])([CH3:47])[CH3:46])=[O:42])[C@H:2]([C:18]([NH:20][C@H:21]([C:23]([NH:25][C@H:26]([C:37]([O:39][CH3:40])=[O:38])[CH2:27][C:28]1[C:36]2[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=2)[NH:30][CH:29]=1)=[O:24])[CH3:22])=[O:19])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1

Participants

4

Reactant 1

HCID 44424692N-Boc-Tyr(Bn)-Ala-Trp-OMe

Product 1

HCID 44424693N-Boc-Tyr-Ala-Trp-OMeYield 76%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

compound NR40. N-Boc-Tyr(Bn)-Ala-Trp-OMe (119 mg, 0.185 mmol) in solution in MeOH (4 mL) was hydrogenated overnight at atmospheric pressure in the presence of 10% Pd on charcoal (30 mg). After filtration, evaporation of the solvent and trituration with ether, N-Boc-Tyr-Ala-Trp-OMe (77 mg, 76%) was obtained as a solid. 1H NMR (300 MHz, DMSO-d6) δ 1.19 (d, J=7 Hz, 3H, CH3), 1.29 (s, 9H, (CH3)3), 2.55 and 2.80 (ABX system, 2H, CH2β), 3.13 and 3.16 (ABX system, 2H, CH2β), 3.55 (s, 3H, OCH3), 4.05 (m, 1H, CHα), 4.35 (m, 1H, CHα), 4.50 (m, 1H, CHα), 6.63 (d, J=8.3 Hz, 2H), 6.83 (d, J=8.6 Hz, 1H), 7.03 (m, 4H), 7.16 (d, J=2.1 Hz, 1H), 7.34 (d, J=7.9 Hz, 1H), 7.47 (d, J=7.8 Hz, 1H), 7.92 (d, J=7.4 Hz, 1H, NH), 8.32 (d, J=7.3 Hz, 1H, NH), 9.14 (s, 1H, OH), 10.86 (s, 1NH). 13C NMR (75 MHz, DMSO-d6) δ 18.4 (CH3); 26.9 (CH2 Trp), 28.1 ((CH3)3), 36.4 (CH2 Tyr), 47.8, 51.7, 53.0, 55.9 (CHα Ala, Tyr, Trp or OCH3), 77.9 (C(CH3)3), 109.1 (aromatic C), 111.4, 114.8, 117.9, 118.4, 120.9, 123.7 (aromatic CH), 127.0, 128.2 (aromatic C), 130.0 (aromatic CH), 136.0 (aromatic C), 155.2, 156.6 (Car-O or CO carbamate), 171.4, 172.0, 172.2 (2 CO amide or CO ester). Anal. Calcd. for C29H36N4O7, 1H2O: C, 61.04; H, 6.71; N, 9.82. Found: C, 61.02; H, 6.62; N, 9.66. HRMS (ESI) calcd for C29H36N4O7Na [(M+Na)+] 575.2482. Found 575.2480.

Workup

  1. filtrationAfter filtration, evaporation of the solvent and trituration with ether

Sources & evidence

ORD record
ord-558366cbd7d44002b45fa081515c7a4a
Source dataset
uspto-grants-2011_04
Patent number
US07919468B2

Reaction notes

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