Benzyl chloroformate → HCID 69654521, compound

HRID 1244002Notes

Reaction equation

HRID 1244002 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[CH2:10][CH2:9][CH:8]([CH3:11])[NH:7][CH:6]1[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:4].[CH2:18]([O:25][C:26](Cl)=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C([O-])(O)=O.[Na+]>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:10][CH2:9][C@@H:8]([CH3:11])[N:7]([C:26]([O:25][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[O:27])[C@H:6]1[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)=[O:4]

Participants

4

Reactant 2

HCID 10387Benzyl chloroformateHCID 69654789HCID 69654789, compound

Product 1

HCID 69654521HCID 69654521, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
0 °C

Procedure

(A mixture of two diastereomers and their enantiomers.) To 6-Methyl-2-phenyl-piperidine-3-carboxylic acid methyl ester (1.63 g, 7.0 mmol) in 20 mL of 10% aqueous NaHCO3 at 0° C. was added benzylchloroformate (1.25 g, 7.35 mmol). The mixture was stirred for 45 minutes at 0° C., and was then warmed to room temperature and stirred for an additional 30 minutes. The mixture was partitioned with ether, and the organic phase was dried over MgSO4 and concentrated. Silica gel chromatography (9:1 hexanes/EtOAc) gave 1.62 g (63%) of the title compound as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.1–7.4 (comp, 20H, both diastereomers), 6.1 (br, 1H, minor diastereomer), 5.74 (d, J=3.6, 1H, major diastereomer), 5.05–5.26 (comp, 8H, both diastereomers), 4.67 (d, J=6.0 Hz, 1H, major diastereomer), 4.57 (m, 1H, minor diastereomer), 4.10–4.20 (m, 2H, major diastereomer), 3.70 (s, 3H, major diastereomer), 3.59 (s, 3H, major diastereomer), 3.29 (app dt, J=4.5, 9.4 Hz, 1H, major diastereomer), 2.85 (m, 1H, minor diastereomer), 2.27 (app dq, J=4.1, 13.7 Hz, minor diastereomer), 1.85–2.15 (comp, 4H, both diastereomers), 1.55–1.80 (comp, 3H, both diastereomers), 1.34 (d, J=6.8 Hz, 3H, major diastereomer), 0.37 (d, J=7.1 Hz, 3H, minor diastereomer); 13C NMR (100 MHz) δ 172.8, 140.0, 136.7, 128.5, 128.4, 128.2, 128.0, 127.8, 127.7, 127.6, 127.2, 127.1, 127.0, 126.9, 126.4, 67.5, 66.9, 65.3, 56.4, 52.0, 47.5, 46.6, 44.3, 42.6, 30.2, 25.6, 22.1, 19.8, 17.2, 16.0; mass spectrum m/e calcd. for M+H=368.2. Found 368.2, 324.2 (base).

Workup

  1. addition(A mixture of two diastereomers and their enantiomers
  2. temperaturewas then warmed to room temperature
  3. stirringstirred for an additional 30 minutes
  4. customThe mixture was partitioned with ether
  5. dry with materialthe organic phase was dried over MgSO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-3ac45fdf075948d6a3b937f2f129f40a
Source dataset
uspto-grants-2006_10
Patent number
US07119207B2

Reaction notes

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