Diazomethane → O-Benzoylhydroxylamine

HRID 487367ノート

反応式

HRID 487367 の反応式
O(O)O.[N+](=C)=[N-].ON=[N+]=[N-].N([Si](C)(C)C)=[N+]=[N-].[C:18]([O:26][N:27]=[N+]=[N-])(=[O:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>CO.[Cl-].[Zn+2].[Cl-]>[C:18]([O:26][NH2:27])(=[O:25])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

参加物

8

反応物 5

HCID 9550DiazomethaneHCID 78378AzidotrimethylsilaneHCID 166717TrioxidaneHCID 18670949Hydroxy azide2 回HCID 57299698Azido benzoate

生成物 1

HCID 191324O-Benzoylhydroxylamine

試薬・触媒・溶媒 2

HCID 3007855Zincchloride触媒HCID 887Methanol溶媒

実験手順

Phenylacetylene is subject to 1) hydroxymethylation followed by 2) Lindlar reduction to yield cis-cinnamyl alcohol. ##STR6## 3) The cis-cinnamyl alcohol is subjected to the titanium-catalyzed epoxidation process to yield (2S,3R)-epoxy alcohol. ##STR7## 4) This epoxy alcohol is oxidized with RuCl3 and NaIO4, and 5) the reaction product converted to the methyl ester of the epoxide with ethereal diazomethane. 6) This methyl ester of the epoxide is transformed into the desired hydroxyazide by epoxide cleavage using azidotrimethylsilane and a catalytic amount of zinc chloride followed by acid hydrolysis. ##STR8## 7) The hydroxy azide is transformed into azido benzoate and hydrogenated in methanol to produce amino benzoate. 8) The amino benzoate is rearranged to give the product. ##STR9## Modifications in this method have also been described by Denis, J. N. et al., "An Improved Synthesis of the Taxol Side Chain and of RP56976", J. Org. Chem 55, 1957-1959 (1990).

出典と根拠

ORDレコード
ord-b96380cebd754560b1493c7a3b2468df
出典データセット
uspto-grants-1994_03
特許番号
US05294737

反応ノート

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