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 406897ノート

反応式

HRID 406897 の反応式
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]

参加物

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 67952979Benzyl ursolate2 回

生成物 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-carboxylate収率 95.2%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒4 回

反応条件

温度
-50 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-7b149d609316422f99880215996b221a
出典データセット
uspto-grants-2014_06
特許番号
US08754068B2

反応ノート

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