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

HRID 500376

反応式

HRID 500376 の反応式
[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]

参加物

8

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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=6.2Hz), 4.21 (br t, 1H, J=6.7Hz), 3.94 (dt, 2H, J=5.9, 1.5Hz), 3.42 (t, 2H, J=5.9Hz), 1.90-1.82 (m, 1H), 1.75-1.57 (m, 3H), 1.42 (s, 9H), 1.21 (d, 3H, J=6.2Hz), 1.19 (d, 3H, J=6.2Hz). LCMS m/z 316 (M+H)+.

後処理

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

出典と根拠

ORDレコード
ord-0da6c4d2ddd24d66b48fc100e9ded9a4
出典データセット
uspto-grants-2010_08
特許番号
US07772183B2

関連ノート

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