Dimethyl Sulfoxide → (4R)-5,5-Dimethyl-2-phenyl-1,3-dioxan-4-carbaldehyde

HRID 1919398Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1919398
[CH3:1][C:2]1([CH3:16])[CH2:7][O:6][CH:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[O:4][C@H:3]1[CH2:14][OH:15].C(N(CC)CC)C.CS(C)=O>ClCCl>[CH3:1][C:2]1([CH3:16])[CH2:7][O:6][CH:5]([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[O:4][C@H:3]1[CH:14]=[O:15]

Komponenten

5

Edukt 3

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 67349301[(4R)-5,5-Dimethyl-2-phenyl-1,3-dioxan-4-yl]methan-1-ol

Produkt 1

HCID 86628866(4R)-5,5-Dimethyl-2-phenyl-1,3-dioxan-4-carbaldehydeAusbeute 75 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Following the general procedure for oxidation reactions of Description 7, 40.2 g (181.9 mmol) of [(4R)-5,5-dimethyl-2-phenyl-1,3-dioxan-4-yl]methan-1-ol (7a) in 1,100 mL of dichloromethane (DCM) in the presence of 126.8 mL (92.1 g, 0.910 mol) of triethylamine and 103.3 mL (113.8 g, 1.456 mol) of dimethylsulfoxide (DMSO) was reacted with 86.9 g (0.55 mol) of sulfur trioxide pyridine complex to afford 38.3 g (96% yield) of the crude title compound (7b). Purification by silica gel column chromatography using mixtures of methyl tert-butyl ether (MTBE) and hexane (Hxn) as eluent (MTBE/Hxn=1:9→MTBE/Hxn=1:6) provided 29.9 g (75% yield) of the title compound (7b) as a colorless liquid. Rf=0.58 (MTBE/Hxn=1:2). 1H NMR (400 MHz, CHCl3): δ=1.04 (s, 3H), 1.27 (s, 3H), 3.69 (d, J=11.6 Hz, 1H), 3.75 (d, J=11.2 Hz, 1H), 3.97 (d, J=1.2 Hz, 1H), 5.56 (s, 1H), 7.35-7.44 (m, 3H), 7.54-7.58 (m, 2H), 9.66 (d, J=1.6 Hz, 1H) ppm. MS (ESI) m/z: 221.0 (M+H)+, 242.9 (M+Na)+. The analytical data for the compound was consistent with that given in the literature (Ito et al., Synthesis, 1993, 137-140).

Aufarbeitung

  1. customwas reacted with 86.9 g (0.55 mol) of sulfur trioxide pyridine complex
  2. customto afford 38.3 g (96% yield) of the crude title compound (7b)
  3. customPurification by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-7e9c77f5960e4732a23067b2710fe0d7
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08168617B2

Notizen zur Reaktion

Wird geladen…