Dimethylformamide → (S)-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-1-(4-trimethylsilylethynyl-phenyl)-ethyl]-[1,3]oxazinan-2-one

HRID 333911ノート

反応式

HRID 333911 の反応式
CCN(CC)CC.[CH3:8][Si:9]([C:12]#[CH:13])([CH3:11])[CH3:10].Br[C:15]1[CH:20]=[CH:19][C:18]([CH:21]([N:23]2[CH2:28][CH2:27][C@:26]([CH2:35][C:36]([OH:39])([CH3:38])[CH3:37])([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[O:25][C:24]2=[O:40])[CH3:22])=[CH:17][CH:16]=1.CN(C)C=O>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)(=O)C.O>[OH:39][C:36]([CH3:37])([CH3:38])[CH2:35][C@@:26]1([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[O:25][C:24](=[O:40])[N:23]([C@H:21]([C:18]2[CH:17]=[CH:16][C:15]([C:13]#[C:12][Si:9]([CH3:11])([CH3:10])[CH3:8])=[CH:20][CH:19]=2)[CH3:22])[CH2:28][CH2:27]1

参加物

9

反応物 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 66869824(S)-3-[1-(4-bromo-phenyl)-ethyl]-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-[1,3]oxazinan-2-one

生成物 1

HCID 66869815(S)-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-3-[(S)-1-(4-trimethylsilylethynyl-phenyl)-ethyl]-[1,3]oxazinan-2-one

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
90 °C

実験手順

CuI (0.18 g), Pd(PPh3)2Cl2 (0.33 g), and NEt3 (2.22 mL) were added successively to a flask charged with a stir bar, trimethylsilylacetylene (1.31 mL), (S)-3-[1-(4-bromo-phenyl)-ethyl]-6-(2-hydroxy-2-methyl-propyl)-6-phenyl-[1,3]oxazinan-2-one (2.00 g), and N,N-dimethylformamide (15 mL) and kept at room temperature under argon atmosphere. The flask was tightly sealed and the mixture was heated to 90° C. The mixture was stirred at 90° C. overnight and then cooled to ambient temperature. Water (80 mL) and ethyl acetate (200 mL) were added and the resulting mixture was filtered over Celite. The organic phase of the filtrate was separated and washed with brine and dried (MgSO4). The solvent was evaporated and the residue was chromatographed on silica gel (cyclohexane/ethyl acetate 3:1->0:1) to afford the title compound as an oil. Yield: 0.27 g (34% of theory); LC-MS (Method 1): tR=4.27 min; Mass spectrum (ESI+): m/z=450 [M+H]+.

後処理

  1. additioncharged with a stir bar
  2. customkept at room temperature under argon atmosphere
  3. customThe flask was tightly sealed
  4. temperaturecooled to ambient temperature
  5. filtrationthe resulting mixture was filtered over Celite
  6. customThe organic phase of the filtrate was separated
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. customThe solvent was evaporated
  10. customthe residue was chromatographed on silica gel (cyclohexane/ethyl acetate 3:1->0:1)

出典と根拠

ORDレコード
ord-8d7fa0c896144992a1e9e69fae94dd81
出典データセット
uspto-grants-2014_11
特許番号
US08883778B2

反応ノート

読み込み中…