(8S,11R,15R)-11-(((9H-fluoren-9-yl)methoxy)carbonylamino)-8-ethyl-2,2-dimethyl-4,10-dioxo-3,6-dioxa-13-thia-9-azahexadecane-15,16-diyl didodecanoate → (5S,8R,12R)-8-amino-12-(dodecanoyloxy)-5-ethyl-7,15-dioxo-3,14-dioxa-10-thia-6-azahexacosan-1-oic acid

HRID 2407884ノート

反応式

HRID 2407884 の反応式
[C:1]([O:14][C@H:15]([CH2:54][O:55][C:56](=[O:68])[CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH3:67])[CH2:16][S:17][CH2:18][C@H:19]([NH:36]C(OCC1C2C=CC=CC=2C2C1=CC=CC=2)=O)[C:20](=[O:35])[NH:21][C@@H:22]([CH2:33][CH3:34])[CH2:23][O:24][CH2:25][C:26](=[O:32])[O:27]C(C)(C)C)(=[O:13])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]>C(O)(C(F)(F)F)=O.C(Cl)Cl>[NH2:36][C@@H:19]([CH2:18][S:17][CH2:16][C@H:15]([O:14][C:1](=[O:13])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])[CH2:54][O:55][C:56](=[O:68])[CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH2:66][CH3:67])[C:20](=[O:35])[NH:21][C@@H:22]([CH2:33][CH3:34])[CH2:23][O:24][CH2:25][C:26]([OH:32])=[O:27]

参加物

4

反応物 1

HCID 86678282(8S,11R,15R)-11-(((9H-fluoren-9-yl)methoxy)carbonylamino)-8-ethyl-2,2-dimethyl-4,10-dioxo-3,6-dioxa-13-thia-9-azahexadecane-15,16-diyl didodecanoate

生成物 1

HCID 53476317(5S,8R,12R)-8-amino-12-(dodecanoyloxy)-5-ethyl-7,15-dioxo-3,14-dioxa-10-thia-6-azahexacosan-1-oic acid

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 6422Trifluoroacetic acid溶媒

実験手順

A solution of (8S,11R,15R)-11-(((9H-fluoren-9-yl)methoxy)carbonylamino)-8-ethyl-2,2-dimethyl-4,10-dioxo-3,6-dioxa-13-thia-9-azahexadecane-15,16-diyl didodecanoate (1 eq, from the previous step) in 50% TFA in DCM (0.05 M) was stirred in open air at 40° C. for 1.5 hours. The mixture was dried under a stream of air and briefly evaporated under high vacuum. The resulting oil was dissolved in 20% piperidine in THF (0.1 mL) and stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate. The reaction mixture was concentrated en vaccuo. The crude mixture was purified by flash chromatography on a COMBIFLASH® system (ISCO) using a gradient of 0-10% methanol in DCM to give the product as a solid. 1H NMR (DMSO-d6): δ 8.30 (d, 1H), 5.11 (m, 1H), 4.27 (dd, 1H), 4.09 (dd, 1H), 3.96 (s, 2H), 3.67-3.76 (m, 2H), 3.37-3.48 (m, 2H), 2.71-2.95 (m, 4H), 2.25-2.28 (m, 4H), 1.23-1.62 (m, 41H), 0.83-0.88 (m, 6H). LRMS [M+H]=689.4.

後処理

  1. customThe mixture was dried under a stream of air
  2. custombriefly evaporated under high vacuum
  3. dissolutionThe resulting oil was dissolved in 20% piperidine in THF (0.1 mL)
  4. additionThe reaction mixture was diluted with ethyl acetate
  5. concentrationThe reaction mixture was concentrated en vaccuo
  6. customThe crude mixture was purified by flash chromatography on a COMBIFLASH® system (ISCO)

出典と根拠

ORDレコード
ord-8515a16a42664f94a5cfb796759f2043
出典データセット
uspto-grants-2014_08
特許番号
US08808703B2

反応ノート

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