(Bis(2-methoxyethyl)amino)sulfur trifluoride → Tert-butyl 3-fluoro-4-[(6-nitrothieno[3,2-b]pyridin-7-yl) amino]piperidine-1-carboxylate

HRID 711967Notes

Reaction equation

HRID 711967 reaction equation
O[CH:2]1[CH:7]([NH:8][C:9]2[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][N:12]=[C:11]3[CH:18]=[CH:19][S:20][C:10]=23)[CH2:6][CH2:5][N:4]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:3]1.COCCN(CCOC)S(F)(F)[F:34]>C(Cl)Cl>[F:34][CH:2]1[CH:7]([NH:8][C:9]2[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][N:12]=[C:11]3[CH:18]=[CH:19][S:20][C:10]=23)[CH2:6][CH2:5][N:4]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:3]1

Participants

4

Reactant 2

HCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 86717435tert-Butyl 3-hydroxy-4-[(6-nitrothieno[3,2-b]pyridin-7-yl)amino]piperidine-1-carboxylate

Product 1

HCID 86717437Tert-butyl 3-fluoro-4-[(6-nitrothieno[3,2-b]pyridin-7-yl) amino]piperidine-1-carboxylateYield 44.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of tert-butyl 3-hydroxy-4-[(6-nitrothieno[3,2-b]pyridin-7-yl)amino]piperidine-1-carboxylate (716 mg, 1.82 mmol) in methylene chloride (4 mL) cooled at 0° C. was added slowly 2-methoxy-N-(2-methoxyethyl)-N-(trifluoro-λ(4)-sulfanyl)ethanamine (0.50 mL, 2.7 mmol). The reaction was stirred at room temperature for 4 h. The mixture was diluted with dichloromethane, washed with water, and concentrated. The residue was purified on silica gel (eluting with 0 to 30% EtOAc in dichloromethane) to give the desired product (0.32 g, 44%) as a mixture of cis- and trans-isomers mixture. LCMS calculated for C17H22FN4O4S (M+H)+: m/z=397.1. Found: 397.1.

Workup

  1. washwashed with water
  2. concentrationconcentrated
  3. customThe residue was purified on silica gel (eluting with 0 to 30% EtOAc in dichloromethane)

Sources & evidence

ORD record
ord-d0efdf1e06854380a25dc964e781524c
Source dataset
uspto-grants-2015_11
Patent number
US09181271B2

Reaction notes

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