Tetrabutylammonium Fluoride → Tert-butyl 4-(3-hydroxyprop-1-yn-1-yl)-4-((methoxycarbonyl)oxy)piperidine-1-carboxylate

HRID 2202385Notes

Reaction equation

[Si]([O:8][CH2:9][C:10]#[C:11][C:12]1([O:25][C:26]([O:28][CH3:29])=[O:27])[CH2:17][CH2:16][N:15]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:13]1)(C(C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[OH:8][CH2:9][C:10]#[C:11][C:12]1([O:25][C:26]([O:28][CH3:29])=[O:27])[CH2:13][CH2:14][N:15]([C:18]([O:20][C:21]([CH3:24])([CH3:22])[CH3:23])=[O:19])[CH2:16][CH2:17]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of tert-butyl 4-(3-((tert-butyldimethylsilyl)oxy)prop-1-yn-1-yl)-4-((methoxycarbonyl)oxy)piperidine-1-carboxylate (450 mg, 1.02 mmol) in 30 mL of anhydrous THF was added TBAF (800.5 mg, 3.06 mmol) at 0° C. under N2. After stirring for 1 h at 0° C., the reaction mixture was quenched by sat. NH4Cl aq., and the resulting mixture was extracted with EtOAc (50 mL, 30 mL). The combined organic phase was washed with brine, dried over anhy. Na2SO4 and concentrated in vacuo. Column chromatography (15% PE/EtOAc) afforded 290 mg of title compound. MS (ES) M+H expected 313.25. found 313.47. 1H NMR (CHLOROFORM-d) δ: 4.36 (s, 2H), 4.21 (q, J=7.1 Hz, 2H), 3.80-3.70 (m, 2H), 3.41-3.29 (m, 2H), 2.24-2.13 (m, 2H), 2.00 (ddd, J=13.2, 9.3, 3.9 Hz, 2H), 1.95 (s, 1H), 1.48 (s, 9H), 1.34 (t, J=7.1 Hz, 3H).

Workup

customthe reaction mixture was quenched by sat. NH4Cl aq.
extractionthe resulting mixture was extracted with EtOAc (50 mL, 30 mL)
washThe combined organic phase was washed with brine
customdried over anhy
concentrationNa2SO4 and concentrated in vacuo

Sources & evidence

ORD record: ord-9448cbf840854b65b9ab1d81fa97f31d
Source dataset: uspto-grants-2016_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09365545B2

Reaction notes

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