p-Toluenesulfonic acid → (2S,4R)-4-(Bromomethyl)-2-(Diethoxyphosphinoylmethyl)-1,3-Dioxolane

HRID 636883

반응식

HRID 636883 반응식
[CH2:1]([O:3][CH:4]([O:14][CH2:15][CH3:16])[CH2:5][P:6]([O:11][CH2:12][CH3:13])([O:8][CH2:9][CH3:10])=[O:7])C.[Br:17]C[C@H](O)CO.CC1C=CC(S(O)(=O)=O)=CC=1.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1>[Br:17][CH2:16][C@H:15]1[CH2:1][O:3][C@H:4]([CH2:5][P:6]([O:8][CH2:9][CH3:10])([O:11][CH2:12][CH3:13])=[O:7])[O:14]1

참가 물질

6

반응물 4

HCID 6101p-Toluenesulfonic acidHCID 82071Diethyl (2,2-diethoxyethyl)phosphonateHCID 516892Sodium BicarbonateHCID 2733893(2R)-3-Bromo-1,2-propanediol

생성물 1

HCID 53652584(2S,4R)-4-(Bromomethyl)-2-(Diethoxyphosphinoylmethyl)-1,3-Dioxolane수율 97%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

To a solution of diethylphosphonoacetaldehyde diethylacetal (4.20 g, 16.5 mmol) and (2R)-3-bromo-1,2-propanediol (example 90) (3.00 g, 19.4 mmol, 1.2 eq.) in toluene (30 mL) was added pTSA (few crystals). The mixture was stirred at reflux for 50 hr. After, the solution was cooled to room temperature, and a saturated solution of sodium bicarbonate was added, and the aqueous phase was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure. The crude material was pure by TLC and NMR, and gave 5.06 g of the compound in a 97% yield. 1H NMR (300 MHz, CDCl3) δ: 1.33 (t, 6H, J=7.0 Hz, CH3), 2.20 (dd, 0.66H, J=5.4 Hz, 2JHP=18 Hz, CH2P for trans), 2.25 (dd, 1.33H, J=5.2 Hz, 2JHP=18.7 Hz, CH2P for cis), 3.32 (2dd, 1H, J=7.9 Hz, 10.2 Hz, CHAHBBr), 3.42 and 3.48 (2dd, 1H, J=4.8 Hz, 10.2 Hz, CHAHBBr), 3.74 (dd, 0.33H, J=6.4 Hz, 8.8 Hz, H-5a for trans), 3.99 (d, 1.33H, J=5.2 Hz, H-5 for cis), 4.13 (m, 4H, CH2), 4.26 (dd, 0.33H, J=6.4 Hz, 8.8 Hz, H-5b for trans), 4.35 (m, 1H, H-4), 5.24 (dt, 0.66H, J=5.2 Hz, 3JHP=4.7 Hz, H-2 for cis), 5.37 (dt, 0.33H, J=5.2 Hz, 3JHP=5.2 Hz, H-2 for trans).

후처리

  1. temperatureat reflux for 50 hr
  2. extractionthe aqueous phase was extracted with dichloromethane
  3. dry with materialThe organic layer was dried over anhydrous sodium sulphate
  4. customevaporated under reduced pressure

출처 및 근거

ORD 기록
ord-e4d40b7498594073b779eef2072c9ff3
출처 데이터셋
uspto-grants-2001_02
특허 번호
US06194576B1

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