Trimethylsilyl cyanide → HCID 13521702、化合物

HRID 2121002ノート

反応式

HRID 2121002 の反応式
ClC1C=CC=CC=1[NH:8][CH2:9][C:10]([OH:12])=[O:11].[Cl:13][C:14]1[CH:36]=[CH:35][CH:34]=[CH:33][C:15]=1[CH:16]([NH:19][CH:20]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:17]#[N:18].[Cl:37][C:38]1[CH:45]=[C:44]([Cl:46])[CH:43]=[C:40]([CH:41]=[O:42])[C:39]=1[OH:47].[NH2:48][C@H:49]([C:54]([OH:56])=[O:55])[C:50]([CH3:53])([CH3:52])[CH3:51].[C:57]([O:61][C@H:62]([CH3:68])[C@@H:63]([C:65]([OH:67])=[O:66])[NH2:64])([CH3:60])([CH3:59])[CH3:58].NCC(O)=O.C[Si](C#N)(C)C>C1(C)C=CC=CC=1.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4].CCOCC>[Cl:37][C:38]1[CH:45]=[C:44]([Cl:46])[CH:43]=[C:40]([CH:41]=[O:42])[C:39]=1[OH:47].[NH2:48][C@H:49]([C:54]([OH:56])=[O:55])[C:50]([CH3:53])([CH3:52])[CH3:51].[C:57]([O:61][C@H:62]([CH3:68])[C@@H:63]([C:65]([OH:67])=[O:66])[NH2:64])([CH3:60])([CH3:58])[CH3:59].[CH3:14][O:12][C:10](=[O:11])[CH2:9][NH2:8].[Cl:13][C:14]1[CH:36]=[CH:35][CH:34]=[CH:33][C:15]=1[CH:16]([NH:19][CH:20]([C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:17]#[N:18]

参加物

9

反応物 4

HCID 82115Trimethylsilyl cyanideHCID 247831D-(2-Chlorophenyl)glycineHCID 13521702HCID 13521702、化合物HCID 131724342HCID 131724342、化合物

生成物 2

HCID 13521702HCID 13521702、化合物HCID 131724341HCID 131724341、化合物

試薬・触媒・溶媒 3

HCID 11026Titanium isopropoxide触媒HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

実験手順

The following is an example of a solution phase catalyzed reaction to synthesize 2-chlorophenyl glycine. Screening of the above library determined that a preferred catalyst for the formation of N-(2-chloro-a-cyanobenzyl)benzhydrylamine was 3,5-Dichlorosalicylaldehyde-tert-Leucine-(O-tert-Butyl)Threonine-Glycine. 3,5-Dichlorosalicylaldehyde-tert-Leucine-(O-tert-Butyl)Threonine-Glycine methyl ester was synthesized using standard solid-phase synthesis techniques and was added (53.3 mg, 0.1 mmol) under a nitrogen atmosphere to a solution of titanium tetraisopropoxide (29.5 ul, 0.1 mmol) in toluene (2 ml), and the mixture was stirred for about 15 minutes. Ortho-chlorobenzylidenylbenzhydrylamine (306 mg, 1.0 mmol) was added and the mixture stirred until complete dissolution of the substrate (ca. 10 minutes). Trimethylsilylcyanide (267 ul, 2.0 mmol) was added to the solution and the resultant mixture was stirred for 48 hours. Addition of ether (2 ml, 5% water) followed by filtration through silica afforded a product that was predominantly the desired isomer contaminated with a small amount of starting material. Addition of hexanes to the ethereal solution afforded pure N-(2-chloro-a-cyanobenzyl)benzhydrylamine as white crystals. Analysis by HPLC indicated optical purity of >99%.

後処理

  1. customreaction
  2. customsolid-phase synthesis techniques
  3. additionOrtho-chlorobenzylidenylbenzhydrylamine (306 mg, 1.0 mmol) was added
  4. stirringthe mixture stirred until complete dissolution of the substrate (ca. 10 minutes)
  5. filtrationfollowed by filtration through silica
  6. customafforded a product that

出典と根拠

ORDレコード
ord-d828bf5350344ca8979612e41b33de9a
出典データセット
uspto-grants-2004_02
特許番号
US06693168B1

反応ノート

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