4-Nitrobenzoic Acid → Di-tert-butyl (1S,2R,3S,4S,5R,6R)-2-[(tert-butoxycarbonyl)amino]-3-[(3,4-dichlorobenzyl)oxy]-4-{[(4-nitrophenyl)carbonyl]oxy}bicyclo[3.1.0]hexane-2,6-dicarboxylate

HRID 2172989노트

반응식

HRID 2172989 반응식
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:20]([C:23]1[CH:31]=[CH:30][C:26]([C:27]([OH:29])=[O:28])=[CH:25][CH:24]=1)([O-:22])=[O:21].[C:32]([O:36][C:37]([NH:39][C@@:40]1([C:64]([O:66][C:67]([CH3:70])([CH3:69])[CH3:68])=[O:65])[C@H:45]([O:46][CH2:47][C:48]2[CH:53]=[CH:52][C:51]([Cl:54])=[C:50]([Cl:55])[CH:49]=2)[C@H:44](O)[C@@H:43]2[C@H:41]1[C@H:42]2[C:57]([O:59][C:60]([CH3:63])([CH3:62])[CH3:61])=[O:58])=[O:38])([CH3:35])([CH3:34])[CH3:33].N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.C(OCC)C>[C:32]([O:36][C:37]([NH:39][C@@:40]1([C:64]([O:66][C:67]([CH3:70])([CH3:69])[CH3:68])=[O:65])[C@H:45]([O:46][CH2:47][C:48]2[CH:53]=[CH:52][C:51]([Cl:54])=[C:50]([Cl:55])[CH:49]=2)[C@@H:44]([O:28][C:27]([C:26]2[CH:25]=[CH:24][C:23]([N+:20]([O-:22])=[O:21])=[CH:31][CH:30]=2)=[O:29])[C@@H:43]2[C@H:41]1[C@H:42]2[C:57]([O:59][C:60]([CH3:62])([CH3:61])[CH3:63])=[O:58])=[O:38])([CH3:35])([CH3:33])[CH3:34]

참가 물질

7

반응물 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 86695972Di-tert-butyl (1S,2R,3S,4R,5R,6R)-2-[(tert-butoxycarbonyl)amino]-3-[(3,4-dichlorobenzyl)oxy]-4-hydroxybicyclo[3.1.0]hexane-2,6-dicarboxylate

생성물 1

HCID 86695973Di-tert-butyl (1S,2R,3S,4S,5R,6R)-2-[(tert-butoxycarbonyl)amino]-3-[(3,4-dichlorobenzyl)oxy]-4-{[(4-nitrophenyl)carbonyl]oxy}bicyclo[3.1.0]hexane-2,6-dicarboxylate수율 51%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매2회

실험 절차

Triphenylphosphine (12.66 g, 48.26 mmol) and 4-nitrobenzoic acid (8.19 g, 48.26 mmol) are added to di-tert-butyl (1S,2R,3S,4R,5R,6R)-2-[(tert-butoxycarbonyl)amino]-3-[(3,4-dichlorobenzyl)oxy]-4-hydroxybicyclo[3.1.0]hexane-2,6-dicarboxylate (14.20 g, 24.13 mmol) and tetrahydrofuran (241.28 mL, 2.97 moles) at room temperature. Cool the mixture in an ice bath. Diisopropyl azodicarboxylate (9.57 mL, 9.76 g, 48.26 mmol) in tetrahydrofuran (20 mL) is added and the reaction mixture is gradually warmed to room temperature overnight. Dilute with diethyl ether, and then wash with aqueous sodium carbonate. Extract the aqueous layer again with diethyl ether. Combine all ether extracts, wash with water, brine, dry over magnesium sulfate, and concentrate under reduced pressure to give a residue. The residue is purified by flash chromatography, eluting with 10-100% ethyl acetate in hexanes to give the title compound (9 g, 12.2 mmol, 51%): MS (m/z): 759 (M+1).

후처리

  1. temperatureCool the mixture in an ice bath
  2. washwash with aqueous sodium carbonate
  3. extractionExtract the aqueous layer again with diethyl ether
  4. washwash with water, brine
  5. dry with materialdry over magnesium sulfate
  6. concentrationconcentrate under reduced pressure
  7. customto give a residue
  8. customThe residue is purified by flash chromatography
  9. washeluting with 10-100% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-1eba926459354bfc9448b07d66cfd221
출처 데이터셋
uspto-grants-2015_06
특허 번호
US09056844B2

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