Propargyl alcohol → (s)-Methyl 2-acetamido-3-(prop-2-ynyloxy)propanoate

HRID 1425691Notes

Reaction equation

[C:1]([N@:4]1[CH2:6][CH:5]1[C:7]([O:9][CH3:10])=[O:8])(=[O:3])[CH3:2].[CH2:11]([OH:14])[C:12]#[CH:13].B(F)(F)F.CCOCC>>[C:1]([NH:4][C@@H:5]([CH2:6][O:14][CH2:11][C:12]#[CH:13])[C:7]([O:9][CH3:10])=[O:8])(=[O:3])[CH3:2]

Participants

Reactant 3

HCID 7859Propargyl alcohol

HCID 8000Boron trifluoride etherate

HCID 21609344Methyl 1-acetylaziridine-2-carboxylate

Product 1

HCID 44542821(s)-Methyl 2-acetamido-3-(prop-2-ynyloxy)propanoateYield 63.2%

Procedure

Using (S)-methyl 1-acetylaziridine-2-carboxylate (1.50 g, 10.49 mmol), propargyl alcohol (0.92 mL, 15.74 mmol) and BF3.Et2O (1.39 mL, 11.01 mmol), and the preceding procedure gave 1.32 g (63%) of desired product as a white solid: mp 59-59.5° C.; [α]25D +65.3° (c 1, CHCl3); Rf=0.35 (3/1 EtOAc/hexanes); IR (nujol mull) 3296, 2924, 2116, 1740, 1641, 1543, 1457 cm−1; 1H NMR (CDCl3) δ 2.06 (s, CH3C(O)), 2.46 (t, J=2.4 Hz, CH2CCH), 3.78 (s, OCH3), 3.79 (dd, J=3.2, 9.4 Hz, CHH′OCH2), 3.98 (dd, J=3.0, 9.4 Hz, CHH′OCH2), 4.12 (½HH′q, J=2.4, 16.2 Hz, OCHH′C), 4.18 (½HH′q, J=2.4, 16.2 Hz, OCHH′C), 4.77-4.82 (m, CH), 6.32-6.34 (br d, J=7.2, NHCH); 13C NMR (CDCl3) δ 23.3 (CH3C(O)), 52.6 (CH), 52.8 (OCH3), 58.7 (CH2CCH), 69.6 (CH2OCH2), 75.3 (CH2CCH), 79.0 (CH2CCH), 170.1, 170.7 (2 C(O)); HRMS (ESI) 200.0917 [M+H+] (calcd. for C9H14NO4 200.0923); Anal. (C9H13NO4) Calcd.: C, 54.26%; H, 6.58%; N, 7.03%. Found: C, 54.05%; H, 6.55%; N, 6.95%.

Sources & evidence

ORD record: ord-6478411cdaa147a7af38df3e1febb224
Source dataset: uspto-grants-2015_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08933065B2

Reaction notes

Loading…