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

HRID 2215978Notes

Reaction equation

HRID 2215978 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-49568a1459204f2ab3e334ec0691035f
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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