Pyridine → HCID 66850227, compound

HRID 131620Notes

Reaction equation

HRID 131620 reaction equation
[CH2:1]([O:8][CH2:9][CH:10]([CH3:29])[CH:11]([OH:28])[CH:12]([CH3:27])[C:13](=[O:26])[C:14]([CH3:25])([CH3:24])[CH:15]([O:20][CH:21]([CH3:23])[CH3:22])[O:16][CH:17]([CH3:19])[CH3:18])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.Cl[C:37]([O:39][CH2:40][C:41]([Cl:44])([Cl:43])[Cl:42])=[O:38]>C(Cl)Cl>[Cl:42][C:41]([Cl:44])([Cl:43])[CH2:40][O:39][C:37](=[O:38])[O:28][CH:11]([CH:10]([CH3:29])[CH2:9][O:8][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[CH:12]([CH3:27])[C:13](=[O:26])[C:14]([CH3:24])([CH3:25])[CH:15]([O:20][CH:21]([CH3:22])[CH3:23])[O:16][CH:17]([CH3:19])[CH3:18]

Participants

5

Reactant 3

HCID 1049PyridineHCID 870632,2,2-Trichloroethyl chloroformateHCID 20817571HCID 20817571, compound

Product 1

HCID 66850227HCID 66850227, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 7-Benzyloxy-5-hydroxy-1,1-diisopropoxy-2,2,4,6-tetramethyl-heptan-3-one (1.0 g, 2.4 mmol) and pyridine (0.8 mL, 7.3 mmol) in CH2Cl2 (10.0 mL) at 0° C. was added 2,2,2-trichloroethyl chloroformate (668.0 μL, 4.9 mmol) and the mixture was then allowed to warm to rt. After 1 h, the reaction mixture was quenched with brine and then extracted with CH2Cl2. The combined organic layers were dried over MgSO4 and concentrated under reduced pressure. The crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 93:7) to give the desired product (1.285 g, 92%) as a clear oil: 1H NMR (400 MHz, CDCl3) δ 1.03-1.09 (m, 12H), 1.15 (d, J=1.8 Hz, 3H), 1.17 (d, J=1.9 Hz, 3H), 1.19-1.21 (m, 6H), 1.97-2.11 (m, 1H), 3.2 (dd, J=6.2 and 9.0 Hz, 1H), 3.54 (dd, J=4.8 and 9.1 Hz, 1H), 3.57-3.60 (m, 1H), 3.82 (qd, J=3.6 and 5.9 Hz, 2H), 4.47 (s, 2H), 4.57 (s, 1H), 4.72 (d, J=11.9 Hz, 1H), 4.81 (d, J=11.9 Hz, 1H), 5.08 (t, J=6.0 Hz, 1H), 7.29-7.35 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 11.9, 15.0, 18.8, 21.4, 21.7, 22.3, 23.2, 23.4, 35.7, 42.5, 53.4, 53.9, 69.4, 70.9, 71.4, 73.3, 81.3, 94.7, 103.4, 127.5, 127.6, 128.2, 138.2, 154.0, 215.6; IR (film, NaCl, cm−1) 2966, 1760, 1698, 1247; LRMS (ESI) calcd for C27H41O7Cl3Na [M+Na+] 605.2, found 605.2; [α]23D=−20.4 (c=1.0, CHCl3.

Workup

  1. customthe reaction mixture was quenched with brine
  2. extractionextracted with CH2Cl2
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 93:7)

Sources & evidence

ORD record
ord-f5d8a44cae69487ab6787f24dd0942f2
Source dataset
uspto-grants-2008_06
Patent number
US07384964B2

Reaction notes

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