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Benzyl Alcohol → HCID 68856283, Verbindung

HRID 2110518
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2110518
C(OC(=O)C[C@@H:8]([NH:16][C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18])[CH2:9]C(C)(C)CCC)(C)(C)C.C(OC(=O)C[CH:35]([CH2:39][C:40]([CH3:45])([CH3:44])[CH2:41][CH2:42][CH3:43])[C:36]([OH:38])=O)(C)(C)C.C1C=CC(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)=CC=1.C(O)C1C=CC=CC=1>CCN(CC)CC>[CH3:45][C:40]([CH3:44])([CH2:41][CH2:42][CH3:43])[CH2:39][CH2:35][C:36]([N:16]1[C@@H:8]([CH3:9])[C@@H:20]([C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[O:19][C:17]1=[O:18])=[O:38]
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Komponenten

6

Edukt 4

HCID 244Benzyl AlcoholHCID 199401P,P-Diphenylphosphinic azideHCID 68856262HCID 68856262, VerbindungHCID 876026502-(2,2-Dimethyl-pentyl)-succinic acid 4-tert-butyl ester

Produkt 1

HCID 68856283HCID 68856283, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8471
Triethylamine
Lösungsmittel

Versuchsvorschrift

A solution of 4,4-dimethyl-heptanoic acid (1.58 g, 10 mmol) and triethylamine (4.6 mL) in 50 mL THF was cooled to 0° C. and treated with 2,2-dimethyl-propionyl chloride (1.36 mL). After one hour, 4R-methyl-5S-phenyl-oxazolidin-2-one (1.95 g, 11 mmol) and lithium chloride (0.47 g, 11 mmol) was added and the mixture was stirred for 18 hours. The precipitate was filtered and washed thoroughly with additional THF. The filtrate was concentrated in vacuo to give an oily solid. This solid was dissolved in 200 mL Et2O, washed successively with saturated NaHCO3, 0.5N HCl and saturated NaCl, dried (MgSO4) and concentrated in vacuo to give the title compound as an oil (3.0 g, 95%). 1HNMR (400 MHz; CDCl3): 0.73-0.84 (m, 12H), 1.10-1.22 (m, 4H), 1.46-1.54 (m, 2H), 2.75-2.87 (m, 2H), 4.70 (m, 1H, J=7 Hz), 5.59 (d, 1H, J=7 Hz), 7.22-7.37 (m, 5H). 5,5-Dimethyl-(S)-3-((R)-4-methyl-2-oxo-(S)-5-phenyl-oxazolidine-3-carbonyl)-octanoic acid tert-butyl ester: According to example 1, 5.07 g (16 mmol) of 3-(4,4-dimethyl-heptanoyl)-4-methyl-5-phenyl-oxazolidin-2-one, 18 mL (1N, 18 mmol) of NaHMDS solution and 4.72 mL (32 mmol) of bromo-acetic acid tert-butyl ester gave 3.40 g (49.3%) of the title compound as a crystalline solid. 1HNMR (400 MHz; CDCl3): 0.85-0.89 (m, 12H), 1.18-1.32 (m, 6H), 1.41 (s, 9H), 1.88 (dd, 1H, J=6 Hz, 8.4 Hz), 2.41 (dd, 1H, J=6 Hz, 16 Hz), 2.62 (dd, 1H, J=8.4 Hz, 16 Hz), 4.30-4.40 (m, 1H), 4.72 (m, 1H), 5.62 (d, 1H, J=7 Hz), 7.30-7.40 (m, 5H). m.p.: 83-85° C. (S)-2-(2,2-Dimethyl-pentyl)-succinic acid 4-tert-butyl ester: According to example 1, 3.4 g (7.9 mmol) of 5,5-dimethyl-3-(4-methyl-2-oxo-5-phenyl-oxazolidine-3-carbonyl)-octanoic acid tert-butyl ester, 16 mL (12.8 mmol) of 0.8N LiOH and 4.5 mL of 30% H2O2 gave 2.42 g (>100%) of the title compound as an oil. 1HNMR (400 MHz; CDCl3): 0.77-0.82 (m, 9H), 1.14-1.29 (m, 5H), 1.42 (s, 9H), 1.77 (dd, 1H, J=8 Hz, 16 Hz), 2.36 (dd, 1H, J=6 Hz, 16 Hz), 2.59 (dd, 1H, J=8 Hz, 16 Hz), 2.75-2.85 (m, 1H). (S)-3-Benzyloxycarbonylamino-5,5-dimethyl-octanoic acid tert-butyl ester: According to example 1, 2.149 (7.9 mmol) of 2-(2,2-dimethyl-pentyl)-succinic acid 4-tert-butyl ester, 1.7 mL of DPPA, 1.1 mL of Et3N and 2.44 mL of BnOH provided 1.639 (54.8% in two steps) of the title compound as an oil. 1HNMR (400 MHz; CDCl3): 0.78-0.89 (m, 9H), 1.10-1.30 (m, 5H), 1.36 (s, 9H), 2.39 (t, 2H, J=5 Hz), 4.95-4.05 (m, 1H), 5.00 (s, 2H), 5.09 (d, 1H, J=9.6 Hz), 7.22-7.30 (m, 5H). (S)-3-Amino-5,5-dimethyl-octanoic acid tert-butyl ester: According to example 1, 1.639 of 3-benzyloxycarbonylamino-5,5-dimethyl-octanoic acid tert-butyl ester and 0.29 of 20% Pd/C furnished the title compound. 1HNMR (400 MHz; CDCl3): 0.84-0.89 (m, 9H), 1.13-1.39 (m, 6H), 1.43 (s, 9H), 2.25 (dd, 1H, J=8.4 Hz, 15.6 Hz), 2.35 (dd, 1H, J=4.4 Hz, 15.6 Hz), 2.79 (s, br, 2H), 3.25-3.35 (m, 1H). MS, m/z, 244.2 (M+1)+. (S)-3-Amino-5,5-dimethyl-octanoic acid hydrochloride: According to example 1,3-amino-5,5-dimethyl-octanoic acid tert-butyl ester was treated with 3N HCl to provide 286 mg of the title compound as a solid. 1HNMR (400 MHz; CD3OD): 0.87-0.93 (m, 9H), 1.18-1.31 (m, 4H), 1.51 (dd, 1H, J=4 Hz, 14.4 Hz), 1.62 (dd, 1H, J=6.8 Hz, 14.4 Hz), 2.60 (dd, 1H, J=8 Hz, 17.6 Hz), 2.73 (dd, 1H, J=4 Hz, 7.6 Hz), 3.55-3.60 (m, 1H). MS (APCl), m/z 188.1 (M+1)+. 186.1 (M−1)+. Anal. Calc'd for C10H21NO2.HCl.0.12H2O: C, 53.17; H, 9.92, N, 6.20, Cl: 15.69; Found: C, 53.19; H, 10.00, N, 6.08, Cl: 15.25. α=+200 (MeOH). MP: 194.2-195.2° C.

Quellen und Nachweise

ORD-Eintrag
ord-723015bcaf7343759498906e4f1f751a
Quelldatensatz
uspto-grants-2009_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07517909B2

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