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

HRID 1027837노트

반응식

HRID 1027837 반응식
[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

참가 물질

4

반응물 1

HCID 58498828HCID 58498828, 화합물

생성물 1

HCID 58498907(S)-Methyl 2-(((benzyloxy)carbonyl)amino)-2-((S)-tetrahydro-2H-pyran-3-yl)acetate수율 65.4%

시약·촉매·용매 2

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

실험 절차

(−)-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 H2, 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, 5 H), 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, 3 H), 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).

후처리

  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)

출처 및 근거

ORD 기록
ord-11fb69046b80449891b24e7f430ee671
출처 데이터셋
uspto-grants-2014_05
특허 번호
US08735398B2

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