Dimethyl Sulfoxide → benzyl (1S,2R,4aS,6aR,6aS,6bR,8aR,12aR,14bS)-1,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,2,3,4,5,6,6a,7,8,8a,11,12,13,14b-tetradecahydropicene-4a-carboxylate

HRID 2405522노트

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HRID 2405522 반응식
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][C@H:12]1[CH2:33][CH2:32][C@@:31]2([CH3:34])[C@@H:14]([CH2:15][CH2:16][C@:17]3([CH3:48])[C@@H:30]2[CH2:29][CH:28]=[C:27]2[C@@:18]3([CH3:47])[CH2:19][CH2:20][C@:21]3([C:37]([O:39][CH2:40][C:41]4[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=4)=[O:38])[C@H:26]2[C@@H:25]([CH3:35])[C@H:24]([CH3:36])[CH2:23][CH2:22]3)[C:13]1([CH3:50])[CH3:49].C(N(CC)CC)C>C(Cl)Cl>[CH3:35][C@@H:25]1[C@@H:26]2[C@@:21]([C:37]([O:39][CH2:40][C:41]3[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=3)=[O:38])([CH2:20][CH2:19][C@:18]3([CH3:47])[C:27]2=[CH:28][CH2:29][C@H:30]2[C@@:17]3([CH3:48])[CH2:16][CH2:15][C@@H:14]3[C@:31]2([CH3:34])[CH2:32][CH2:33][C:12](=[O:11])[C:13]3([CH3:49])[CH3:50])[CH2:22][CH2:23][C@H:24]1[CH3:36]

참가 물질

6

반응물 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 67952979Benzyl ursolate2회

생성물 1

HCID 67952365benzyl (1S,2R,4aS,6aR,6aS,6bR,8aR,12aR,14bS)-1,2,6a,6b,9,9,12a-heptamethyl-10-oxo-1,2,3,4,5,6,6a,7,8,8a,11,12,13,14b-tetradecahydropicene-4a-carboxylate수율 95.2%

시약·촉매·용매 1

HCID 6344Dichloromethane용매4회

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온도
-50 °C

실험 절차

To a solution of oxalyl chloride (2.57 mL, 5.14 mmol) in methylene chloride (5 mL) at −78° C. under nitrogen was added dropwise a solution of DMSO (0.46 mL 6.4 mmol) in methylene chloride (5 mL). The mixture was allowed to warm to −50° C. To this was added a solution of the (1S,2R,4aS,6aS,6bR,8aR,10S,12aR,12bR,14bS)-benzyl 10-hydroxy-1,2,6a,6b,9,9,12a-heptamethyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydropicene-4-a-carboxylate (intermediate A1) (2.34 gm, 4.28 mmol) in methylene chloride (15 mL) forming a white milky suspension. The mixture was stirred for an additional 15 minutes at −50° C. after the addition, it was then treated with triethylamine (1.79 mL, 12.84 mmol) and the reaction mixture was slowly warmed to RT. It was diluted with methylene chloride (100 mL), washed with water (2×100 mL), followed by brine (50 mL). The organic phase was separated out, dried over anhydrous sodium sulfate, and concentrated in vacuo to a syrup. This crude material was partitioned over a silica gel column, eluted with 9:1, hexanes:ethyl acetate solvent to give the title compound as a pale solid (2.22 g, 95%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.69 (s, 3H), 0.87 (d, J=6.53 Hz, 3H), 0.93-0.97 (m, 3H), 1.03 (s, 3H), 1.05 (s, 3H), 1.09 (s, 6H), 1.26-1.40 (m, 4H), 1.40-1.54 (m, 5H), 1.59 (d, J=9.03 Hz, 2H), 1.70 (br. s., 2H), 1.93 (dd, J=9.54, 3.26 Hz, 4H), 1.97-2.08 (m, 2H), 2.29 (d, J=11.04 Hz, 1H), 2.38 (ddd, J=15.94, 6.90, 3.76 Hz, 1H), 2.49-2.61 (m, 1H), 4.97-5.03 (m, 1H), 5.10-5.15 (m, 1H), 5.27 (t, J=3.51 Hz, 1H), 7.31-7.39 (m, 5H).

후처리

  1. customforming a white milky suspension
  2. additionafter the addition, it
  3. temperaturethe reaction mixture was slowly warmed to RT
  4. washwashed with water (2×100 mL)
  5. customThe organic phase was separated out
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo to a syrup
  8. customThis crude material was partitioned over a silica gel column
  9. washeluted with 9:1, hexanes

출처 및 근거

ORD 기록
ord-4992bda77bb9464b8921d4cdd9080d25
출처 데이터셋
uspto-grants-2014_08
특허 번호
US08802661B2

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