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

HRID 514849Notes

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-db1813770d924bdbb17129f9d2d44b52
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09108921B2

Reaction notes

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