Ethanol → tert-butyl 3-methyl-2-[3-[5-[N-[(2-methylpropan-2-yl)oxycarbonyl]carbamimidoyl]-2-methylsulfanylthiophen-3-yl]sulfonylphenyl]benzoate

HRID 723025Notes

Reaction equation

HRID 723025 reaction equation
[C:1]([O:5][C:6](=[O:27])[NH:7][C:8]([C:10]1[S:11][C:12]([S:25][CH3:26])=[C:13]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[C:20](Br)[CH:19]=2)(=[O:17])=[O:16])[CH:14]=1)=[NH:9])([CH3:4])([CH3:3])[CH3:2].[C:28]([O:32][C:33](=[O:50])[C:34]1[CH:39]=[CH:38][C:37](C)=[CH:36][C:35]=1B1OC(C)(C)C(C)(C)O1)([CH3:31])([CH3:30])[CH3:29].[C:51]([O-])([O-])=O.[Na+].[Na+].C(O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[C:28]([O:32][C:33]([C:34]1[C:35]([C:20]2[CH:21]=[CH:22][CH:23]=[C:18]([S:15]([C:13]3[CH:14]=[C:10]([C:8]([NH:7][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:27])=[NH:9])[S:11][C:12]=3[S:25][CH3:26])(=[O:17])=[O:16])[CH:19]=2)=[C:36]([CH3:51])[CH:37]=[CH:38][CH:39]=1)=[O:50])([CH3:29])([CH3:30])[CH3:31]

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 695868564-Methyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid tert-butyl esterHCID 145857672tert-butyl N-[4-(3-bromophenyl)sulfonyl-5-methylsulfanylthiophene-2-carboximidoyl]carbamate2×

Product 1

HCID 145857677tert-butyl 3-methyl-2-[3-[5-[N-[(2-methylpropan-2-yl)oxycarbonyl]carbamimidoyl]-2-methylsulfanylthiophen-3-yl]sulfonylphenyl]benzoateYield 58.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

The procedure used in Example 1: step c was followed using {[4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester (Example 27 (50 mg, 0.1 mmol)), 4-methyl-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid tert-butyl ester ((Example 4: step b) 127 mg, 0.4 mmol), Na2CO3 (2M, 0.8 mL, 1.6 mmol), Pd(PPh3)4 (29.4 mg, 0.025 mmol), ethanol (0.8 mL) and toluene (1.6 mL). Analogous aqueous workup and purification of the crude material by preparative TLC (25% EtOAc in hexanes) yielded the title compound (35 mg, 58%) as a light-yellow glass. 1H-NMR (CDCl3): δ 8.01 (ddd, 1H, J=1.2, 1.9, 7.9 Hz), 7.92 (s, 1H), 7.83 (t, 1H, J=1.7 Hz), 7.65 (m, 1H), 7.56 (t, 1H, J=7.8 Hz), 7.43 (dt, 1H, J=1.4, 7.7 Hz), 7.36 (m, 2H), 2.58 (s, 3H), 2.00 (s, 3H), 1.51 (s, 9H). ESI-MS (m/z): Calcd. for C29H34N2O6S3: 602.8; found: 602.9.

Workup

  1. customAnalogous aqueous workup and purification of the crude material by preparative TLC (25% EtOAc in hexanes)

Sources & evidence

ORD record
ord-6ffc27b9358c432389f811a7fdb6ce76
Source dataset
uspto-grants-2006_11
Patent number
US07138530B2

Reaction notes

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