HCID 58498828, Verbindung → (S)-Methyl 2-(((benzyloxy)carbonyl)amino)-2-((S)-tetrahydro-2H-pyran-3-yl)acetate

HRID 1471103

Reaktionsgleichung

Reaktionsgleichung von HRID 1471103
[CH2:1]([O:8][C:9]([NH:11]/[C:12](=[C:17]1\[CH2:18][O:19][CH2:20][CH2:21][CH2:22]\1)/[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>CO.[B-](F)(F)(F)F.C[C@H]1CC[C@H](C)P1CCP1[C@@H](C)CC[C@@H]1C.C1CC=CCCC=C1.[Rh]>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([C@@H:17]1[CH2:22][CH2:21][CH2:20][O:19][CH2:18]1)[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

4

Edukt 1

HCID 58498828HCID 58498828, Verbindung

Produkt 1

HCID 58498907(S)-Methyl 2-(((benzyloxy)carbonyl)amino)-2-((S)-tetrahydro-2H-pyran-3-yl)acetateAusbeute 65,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 129644171,2-Bis[(2S,5S)-2,5-dimethylphospholano]ethane(cyclooctadiene)rhodium(I) tetrafluoroborateKatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

(−)-1,2-Bis((2S,5S)-2,5-dimethylphospholano)ethane(cyclooctadiene)-rhodium(I)tetrafluoroborate (28.2 mg, 0.051 mmol) was added to a stirred solution of (Z)-methyl 2-(benzyloxycarbonylamino)-2-(2H-pyran-3(4H,5H,6H)-ylidene)acetate (310 mg, 1.015 mmol) in MeOH (10 mL) and the mixture was vacuum flushed with N2, followed by Hz, and then the reaction was stirred under H2 (60 psi) at rt for 2d. The reaction mixture was concentrated and the residue was purified by flash silica chromatography (loading solvent: DCM, eluted with 20% EtOAc in hexanes) to yield (S)-methyl 2-(benzyloxycarbonylamino)-2-((S)-tetrahydro-2H-pyran-3-yl)acetate (204 mg) as clear colorless oil. LC-MS retention time 1.437 min; m/z 307.89 (MH+). LC data was recorded on a Shimadzu LC-10AS liquid chromatograph equipped with a PHENOMENEX® Luna 10u C18 3.0×50 mm column using a SPD-10AV UV-Vis detector at a detector wave length of 220 nM. The elution conditions employed a flow rate of 4 mL/min, a gradient of 100% Solvent A/0% Solvent B to 0% Solvent A/100% Solvent B, a gradient time of 3 min, a hold time of 1 min, and an analysis time of 4 min where Solvent A was 5% MeOH/95% H2O/10 mM ammonium acetate and Solvent B was 5% H2O/95% MeOH/10 mM ammonium acetate. MS data was determined using a MICROMASS® Platform for LC in electrospray mode. 1H NMR (400 MHz, chloroform-d) δ ppm 7.30-7.46 (m, 5H), 5.32 (d, J=8.8 Hz, 1 H), 5.12 (s, 2 H), 4.36 (dd, J=8.9, 5.6 Hz, 1 H), 3.84-3.98 (m, 2 H), 3.77 (s, 3H), 3.28-3.37 (m, 1 H), 3.23 (dd, J=11.3, 10.5 Hz, 1 H), 2.04-2.16 (m, 1 H), 1.61-1.75 (m, 3 H), 1.31-1.43 (m, 1 H).

Aufarbeitung

  1. customflushed with N2
  2. concentrationThe reaction mixture was concentrated
  3. customthe residue was purified by flash silica chromatography (loading solvent: DCM, eluted with 20% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-cb891cc56a104fa588fa54a238987984
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09006455B2

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