应用Atherton-Todd反应进行酪氨酸O-磷酰化  

A Study of Tyrosine O-Phosphorylation via Atherton-Todd Reaction

作　　者：赵刚[1] 李艳梅[1] 罗施中[1] 韩波[1] 赵玉芬[1] 

机构地区：[1]清华大学化学系生命有机磷化学教育部重点实验室,北京100084

出　　处：《高等学校化学学报》2001年第12期2034-2036,共3页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 980 2 0 0 6 )资助

摘　　要：The tyrosine \%O\%\|phosphorylation \%via\% Atherton\|Todd reaction, which was a classical reaction for phosphorylation amines, was first studied in this paper. Reaction of Boc\|Tyr\|OCH\-3, which was selected as model substrate, with three dialkyl \%H\%\|phosphonate diester in the presence of CCl\-4 and triethylamine produced the corresponding tyrosine \%O\%\|phosphorylation products in a high yield(over 80%). The reaction was conducted in anhydrous THF solution and monitored by \{\}\+\{31\}P NMR and TLC. Then reaction of Boc\|Tyr\|OCH\-3 with a complicated H\|phosphonate diester, \%O\%\|3\|acetylthymidin\|5\|yl \%O\%\|isopropyl \%H\%\|phosphonate diester, also gave a good result and this would be an alternative approach for the synthesis of nucleotide \%O\%\|tyrosine (or tyrosine containing peptide) conjugate. Further, the successful \%O\%\|phosphoration of three tyrosine containing protected dipeptides, Boc\|Tyr\|Val\|OCH\-3, Boc\|Ala\|Tyr\|OCH\-3, Boc\|Tyr\|Tyr\|OCH\-3, with diisopropyl \%H\%\|phosphonate diester demonstrated the effectiveness of the method.The tyrosine \%O\%\|phosphorylation \%via\% Atherton\|Todd reaction, which was a classical reaction for phosphorylation amines, was first studied in this paper. Reaction of Boc\|Tyr\|OCH\-3, which was selected as model substrate, with three dialkyl \%H\%\|phosphonate diester in the presence of CCl\-4 and triethylamine produced the corresponding tyrosine \%O\%\|phosphorylation products in a high yield(over 80%). The reaction was conducted in anhydrous THF solution and monitored by \{\}\+\{31\}P NMR and TLC. Then reaction of Boc\|Tyr\|OCH\-3 with a complicated H\|phosphonate diester, \%O\%\|3\|acetylthymidin\|5\|yl \%O\%\|isopropyl \%H\%\|phosphonate diester, also gave a good result and this would be an alternative approach for the synthesis of nucleotide \%O\%\|tyrosine (or tyrosine containing peptide) conjugate. Further, the successful \%O\%\|phosphoration of three tyrosine containing protected dipeptides, Boc\|Tyr\|Val\|OCH\-3, Boc\|Ala\|Tyr\|OCH\-3, Boc\|Tyr\|Tyr\|OCH\-3, with diisopropyl \%H\%\|phosphonate diester demonstrated the effectiveness of the method.

关 键 词：Atherton-Todd反应 二烷基亚磷酸酯 酪氨酸 O-磷酰化 

分 类 号：O629.711[理学—有机化学]