Triacetoxyperiodinane → 2-Benzyl-6-p-tolyl-pyrimidine-4-carbaldehyde

HRID 1917268Notes

Reaction equation

HRID 1917268 reaction equation
[CH2:1]([C:8]1[N:13]=[C:12]([CH2:14][OH:15])[CH:11]=[C:10]([C:16]2[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18][CH:17]=2)[N:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[CH2:1]([C:8]1[N:13]=[C:12]([CH:14]=[O:15])[CH:11]=[C:10]([C:16]2[CH:17]=[CH:18][C:19]([CH3:22])=[CH:20][CH:21]=2)[N:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 66616359(2-Benzyl-6-p-tolyl-pyrimidin-4-yl)-methanol

Product 1

HCID 862573372-Benzyl-6-p-tolyl-pyrimidine-4-carbaldehydeYield 545%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of the product from Step B (0.102 g, 0.35 mmol) in CH2Cl2 (2 mL) was added the Dess-Martin periodinane (0.228, 0.53 mmol). After 30 min, the mixture was diluted satd. aq. NaHCO3 and extracted with CH2Cl2 (2×). The combined organic layers were dried, concentrated, and filtered through a small plug of SiO2 (25% EtOAc in hexanes). The filtrate was concentrated to give 2-benzyl-6-p-tolyl-pyrimidine-4-carbaldehyde (0.55 g, 54%). To a solution of this aldehyde in CH2Cl2 (3 mL) was added dimethylamine (2 M in THF; 0.15 mL, 0.30 mmol) and NaBH(OAc)3 (0.058 mg, 0.27 mmol). After 15 h, the reaction was diluted with CH2Cl2 and washed with 1 N NaOH. The aqueous layer was extracted with CH2Cl2 (1×). The combined organic layers were dried and concentrated. The resulting residue was purified via SiO2 chromatography (1-7% 2 M NH3 in MeOH/CH2Cl2) to give 0.050 g (79%) of the title compound. MS (ESI): exact mass calcd. for C21H23N3, 317.19; m/z found, 318.4 [M+H]+. 1H NMR (CDCl3): 8.02 (d, J=8.2, 2H), 7.66 (s, 1H), 7.22 (d, J=7.5, 2H), 7.31-7.26 (m, 4H), 7.22-7.18 (m, 1H), 4.33 (s, 2H), 3.58 (s, 2H), 2.41 (s, 3H), 2.32 (s, 6H).

Workup

  1. additionthe mixture was diluted satd
  2. extractionaq. NaHCO3 and extracted with CH2Cl2 (2×)
  3. customThe combined organic layers were dried
  4. concentrationconcentrated
  5. filtrationfiltered through a small plug of SiO2 (25% EtOAc in hexanes)
  6. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-4091d36bc1494b36b84596558644acbe
Source dataset
uspto-grants-2013_12
Patent number
US08618288B2

Reaction notes

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