Triphenylphosphine → 1,1-Dimethylethyl 4-{[(6-bromo-3-pyridinyl)oxy]methyl}-1-piperidinecarboxylate

HRID 423518Notes

Reaction equation

HRID 423518 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][N:3]=1.[C:9]([N:16]1[CH2:21][CH2:20][CH:19]([CH2:22]O)[CH2:18][CH2:17]1)([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1COCC1>[Br:1][C:2]1[N:3]=[CH:4][C:5]([O:8][CH2:22][CH:19]2[CH2:20][CH2:21][N:16]([C:9]([O:11][C:12]([CH3:13])([CH3:15])[CH3:14])=[O:10])[CH2:17][CH2:18]2)=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 27628652-Bromo-5-hydroxypyridineHCID 2764081Tert-butyl 4-(hydroxymethyl)piperidine-1-carboxylate

Product 1

HCID 579302011,1-Dimethylethyl 4-{[(6-bromo-3-pyridinyl)oxy]methyl}-1-piperidinecarboxylateYield 83%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

1,1-Dimethylethyl 4-{[(6-bromo-3-pyridinyl)oxy]methyl}-1-piperidinecarboxylate (0.88 g, 83%) was prepared as a light yellow solid from 2-bromo-5-hydroxypyridine (0.50 g, 2.87 mmol), N-Boc-4-piperidinemethanol (0.64 g, 2.87 mmol) and Ph3P (0.77 g, 2.87 mmol) in THF (15 mL) followed by diisopropyl azodicarboxylate (0.62 g, 94%, 2.87 mmol) in THF (5 mL) in a manner similar to Example 1, Step 2. The material was purified by chromatography on a silica gel column eluted with 5 to 20% EtOAc/hexanes. 1H NMR (400 MHz, CDCl3): δ 8.04 (bs, 1H), 7.36 (d, 1H, J=8.8 Hz), 7.15-7.05 (m, 1H), 4.25-4.10 (m, 2H), 3.82 (d, 2H, J=6.1 Hz), 2.80-2.70 (m, 2H), 2.05-1.90 (m, 1H), 1.85-1.75 (m, 2H), 1.46 (s, 9H), 1.35-1.20 (m, 2H); LRMS (ESI), m/z 393/395 (M+Na).

Workup

  1. customThe material was purified by chromatography on a silica gel column
  2. washeluted with 5 to 20% EtOAc/hexanes

Sources & evidence

ORD record
ord-13f305f0e3584750b1134792e5531a61
Source dataset
uspto-grants-2012_01
Patent number
US08101634B2

Reaction notes

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