Water → HCID 53803370, compound

HRID 1589312Notes

Reaction equation

HRID 1589312 reaction equation
[CH2:1]([O:8][C:9](=[O:17])[CH:10](Br)[CH2:11][C:12]([CH3:15])([CH3:14])[CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.COC(=O)[C@@H](C)N.CN1CCOCC1.O>CS(C)=O.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[CH3:13][C:12]([CH3:15])([CH3:14])[CH:11]=[CH:10][C:9]([O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:17]

Participants

7

Reactant 4

HCID 962WaterHCID 79724-MethylmorpholineHCID 11182647Methyl D-alaninate hydrochlorideHCID 20248027HCID 20248027, compound

Product 1

HCID 53803370HCID 53803370, compoundYield 95.9%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

Benzyl-2-bromo-4,4-dimethylpentanoate (20 g) in dry dimethyl sulphoxide (250 ml) was treated with D-alanine methylester hydrochloride (9.33 g), N-methyl morpholine (6.78 g) and tetrabutyl ammonium iodide (24.7 g) at 90° under an atmosphere of argon for 2 days. The reaction mixture was allowed to cool to room temperature, poured into water (500 ml) and the products recovered by extraction into dichloromethane (3×250 ml). The material isolated from the organic extracts was purified by chromatography on silica developed in a gradient of hexane-ether. Elution with 30% ether-hexane afforded benzyl 4,4-dimethylpent-2-enoate (14 g). Elution with 40% ether in hexane afforded the title compound (350 mg) as a gum; (Found: [m+1]+ =322.2022. C18H27N1O4 requires [m+1]+ =322.2018); νmax (film) 1735 cm-1 ; δ(CDCl3) 0.90 (9H, s, C(CH3)3 ); 1.28 (3H, d, J=7 Hz CHCH3); 2.46 and 2.68 (2H, each dd, J=12 and 5 Hz, CH2 (CH3)3); 3.30 (1H, q, J=5 Hz CH-CH3); 3.36 (1H, t, J=5 Hz, CH-CH2); 3.66 (3H, s, OCH3); 5.12 (2H, s, OCH2) and 7.36 (5H, s, C6H5). Elution with 45% ether in hexane afforded benzyl 2-(R)-N-(1-(R)-methoxycarbonylethyl)-amino-4,4-dimethylpentanoate (340 mg); (Found: [m+1]+ =322.2022. C11H27NO4 requires 322.2018); νmax (film) 3360 and 1735 cms-1 ; δ(CDCl3) 0.90 (9H, s, C(CH3)3); 1.28 (3H, d, J=6 Hz, CHCH3 ); 1.44 and 1.72 (2H, each dd, J=5 and 12.5 Hz, CH2); 3.32 (1H, q, J=7 Hz, CHCH3); 3.44 (1H, t, J=6 Hz, CHCH2); 3.69 (3H, s, OCH3), 5.24 (2H, s, OCH2) and 7.36 (5H, m, C6H5).

Workup

  1. customthe products recovered by extraction into dichloromethane (3×250 ml)
  2. customThe material isolated from the organic extracts
  3. customwas purified by chromatography on silica
  4. washElution with 30% ether-hexane

Sources & evidence

ORD record
ord-410597e4134048069b991ddf7bf3bfd1
Source dataset
uspto-grants-1986_02
Patent number
US04568666

Reaction notes

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