dimethyl(S)-(3-methyl-2-oxo-6-phenylhexyl)phosphonate → (R)-(-)-dimethyl (3-methyl-2-oxo-6-phenylhexyl)phosphonate

HRID 59700Notes

Reaction equation

HRID 59700 reaction equation
C[C@H](CCCC1C=CC=CC=1)C(OCC)=O.[CH3:17][C@@H:18]([CH2:28][CH2:29][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)[C:19](=[O:27])[CH2:20][P:21](=[O:26])([O:24][CH3:25])[O:22][CH3:23]>>[CH3:17][C@H:18]([CH2:28][CH2:29][CH2:30][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1)[C:19](=[O:27])[CH2:20][P:21](=[O:26])([O:24][CH3:25])[O:22][CH3:23]

Participants

3

Reactant 2

HCID 90054415dimethyl(S)-(3-methyl-2-oxo-6-phenylhexyl)phosphonateHCID 90054516(R)-(-)-ethyl 2-methyl-5-phenylpentanoate

Product 1

HCID 90054381(R)-(-)-dimethyl (3-methyl-2-oxo-6-phenylhexyl)phosphonateYield 66%

Procedure

(R)-(−)-Dimethyl (3-methyl-2-oxo-6-phenylhexyl)phosphonate was prepared from 14mc(i) (93 mg) in the same manner (S)-(+)-dimethyl (3-methyl-2-oxo-6-phenylhexyl)phosphonate was prepared from 14mb(i) as described above. The residue was purified by silica gel chromatography. Elution with ethyl acetate-heptane (70:30 v/v) afforded the title compound (83 mg, 66%) as a colorless oil; TLC Rf 0.22 (solvent system: 70:30 v/v ethyl acetate-heptane); HPLC retention time 12.36 min, 5μ Chiralpak OJ-H 4.6×250 mm, at ultraviolet wavelength of 210 nm, 90:10:0.1 heptane-ethanol:acetic acid) 1 mL/min, chiral purity 100% (R); MS (ESI−) m/z 297.1 (M−H)−; 1H NMR (CDCl3) δ 7.29 (d, J=6.51 Hz, 2H,), 7.22-7.16 (m, 3H), 3.77 (d, J=11.35 Hz, 3H), 3.78 (d, J=11.35 Hz, 3H), 3.13 (d, J=1.83 Hz, 1H), 3.08 (d, J=1.83 Hz, 1H), 2.78 (d, J=6.96 Hz, 1H), 2.67-2.56 (m, 2H), 1.61-1.52 (m, 3H), 1.45-1.32 (m, 1H), 1.11 (d, J=6.96 Hz, 3H); [α]Tλ=α/cl, [α]21.9D=−0.080/(0.01742 g/1.5 mL)(0.5)=−13.78° (c=1.16, CHCl3).

Workup

  1. customwas prepared from 14mb(i)
  2. customThe residue was purified by silica gel chromatography
  3. washElution with ethyl acetate-heptane (70:30 v/v)

Sources & evidence

ORD record
ord-bb9e621966c64a42bcd7c4eca6a78e80
Source dataset
uspto-grants-2016_09
Patent number
US09440919B2

Reaction notes

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