Diisopropylethylamine → HCID 136378615, compound

HRID 2277030Notes

Reaction equation

HRID 2277030 reaction equation
[OH:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:17])[CH2:9][CH2:10]/[CH:11]=[CH:12]/[C:13]([O:15][CH3:16])=[O:14])[O:5][C:4](=[O:18])[C:3]=1[C:19](=[O:22])[CH2:20][CH3:21].CCN(C(C)C)C(C)C.[CH3:32]/[C:33](/[CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])=[CH:34]\[CH:35]=O>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[CH3:21]/[C:20](=[CH:35]\[CH:34]=[C:33]([CH3:32])[CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])/[C:19]([C:3]1[C:4](=[O:18])[O:5][C:6]([CH:8]([CH3:17])[CH2:9][CH2:10]/[CH:11]=[CH:12]/[C:13]([O:15][CH3:16])=[O:14])=[CH:7][C:2]=1[OH:1])=[O:22]

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 12453921HCID 12453921, compoundHCID 54685512HCID 54685512, compound

Product 1

HCID 136378615HCID 136378615, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To (E)-methyl 6-(4-hydroxy-2-oxo-3-propionyl-2-H-pyran-6-yl)hept-2-enoate (VII; 0.63 g, 2.05 mmol) in 30 ml anhydrous CH2Cl2 at −72° C., was added titanium tetrachloride (0.88 ml; 8 mmol; Aldrich) under argon, and the reaction mixture was stirred for 20 min. DIPEA (1.64 ml; 9.43 mmol; Aldrich) was added, and the reaction mixture was stirred for 90 min. (E)-3-methyl-octenal (XXI; 1 g; 7.25 mmol) in 5 ml anhydrous CH2Cl2 was added in two portions over 10 min, and the reaction mixture was stirred at −72° C. for 48 h and at 0° C. for 1 hour. The reaction was quenched with 40 ml ice water and extracted with 2×40 ml CH2Cl2. The CH2Cl2 extracts were pooled, washed with saturated NH4Cl, washed twice with saturated NaHCO3, and dried with anhydrous Na2SO4. The product was purified by silica flash chromatography (EtOAc gradient in hexanes).

Workup

  1. additionwas added in two portions over 10 min
  2. stirringthe reaction mixture was stirred at −72° C. for 48 h and at 0° C. for 1 hour
  3. customThe reaction was quenched with 40 ml ice water
  4. extractionextracted with 2×40 ml CH2Cl2
  5. washwashed with saturated NH4Cl
  6. washwashed twice with saturated NaHCO3
  7. dry with materialdried with anhydrous Na2SO4
  8. customThe product was purified by silica flash chromatography (EtOAc gradient in hexanes)

Sources & evidence

ORD record
ord-b5847088cd56408a8739a119c11ca9a1
Source dataset
uspto-grants-2015_09
Patent number
US09133155B2

Reaction notes

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