Methyl 2-propen-1-yl carbonate → isopropyl 5-allyloxy-2(S)-(tert-butoxycarbonylamino)pentanoate

HRID 17817

반응식

HRID 17817 반응식
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:16][CH2:17][CH2:18][OH:19])[C:10]([O:12][CH:13]([CH3:15])[CH3:14])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)(OC)O[CH2:22][CH:23]=[CH2:24].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CCOCC.CCCCCC>C1COCC1.CCOCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:24]([O:19][CH2:18][CH2:17][CH2:16][C@H:9]([NH:8][C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[C:10]([O:12][CH:13]([CH3:15])[CH3:14])=[O:11])[CH:23]=[CH2:22]

참가 물질

8

반응물 4

HCID 534788Methyl 2-propen-1-yl carbonateHCID 634876Binap, (A+-)-HCID 21080142isopropyl 2(S)-(tert-butoxycarbonylamino)-5-hydroxypentanoateHCID 21584099Diethylether hexane

생성물 1

HCID 21080143isopropyl 5-allyloxy-2(S)-(tert-butoxycarbonylamino)pentanoate

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

실험 절차

A degassed mixture of isopropyl 2(S)-(tert-butoxycarbonylamino)-5-hydroxypentanoate (product of step 26C, 17.6 g, 63.9 mmol), allyl methyl carbonate (24.0 ml, 213 mmol), Pd2(dba)3 (1.62 g, 1.78 mmol) and BINAP (4.42 g, 7.10 mmol) in THF (150 mL) was refluxed under nitrogen for 3 hours. After cooling to room temperature, the reaction was diluted with ether, filtered through celite and evaporated giving a dark brown syrup. Flash chromatography of the residue (silica gel, 30% ether/hexane) gave isopropyl 5-allyloxy-2(S)-(tert-butoxycarbonylamino)pentanoate as a viscous colorless oil, 16.3 g (81%): 1H NMR (300 MHz, Chloroform-D) δ 5.88 (ddt, 1H, 17.4, 10.4, 5.5), 5.28 (m, 1H), 5.22-5.11 (m, 1H), 5.02 (sept., 1H, J=6.2 Hz), 4.21 (br t, 1H, J=6.7 Hz), 3.94 (dt, 2 H, J=5.9, 1.5 Hz), 3.42 (t, 2H, J=5.9 Hz), 1.90-1.82 (m, 1H), 1.75-1.57 (m, 3H), 1.42 (s, 9H), 1.21 (d, 3H, J=6.2 Hz), 1.19 (d, 3H, J=6.2 Hz). LCMS m/z 316 (M+H)+.

후처리

  1. temperaturewas refluxed under nitrogen for 3 hours
  2. filtrationfiltered through celite
  3. customevaporated
  4. customgiving a dark brown syrup

출처 및 근거

ORD 기록
ord-d17b8ec878fd46fc8abb92f0f4d5a39f
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07741281B2

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