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

HRID 1671401ノート

反応式

HRID 1671401 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-d64d4a16599c4f199e003c04db39b963
出典データセット
uspto-grants-2011_08
特許番号
US07994218B2

反応ノート

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