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

HRID 1919398Notes

Reaction equation

HRID 1919398 reaction equation
[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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-7e9c77f5960e4732a23067b2710fe0d7
Source dataset
uspto-grants-2012_05
Patent number
US08168617B2

Reaction notes

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