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 mode...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.展开更多
Six kinds of phosphorylated coumarins are successfully synthesized by an Atherton-Todd reaction. They are fully characterized by FTIR、1H NMR、31P NMR、ESI-MS and EA. For the 6,7-dihydroxy coumarin, there was selectiv...Six kinds of phosphorylated coumarins are successfully synthesized by an Atherton-Todd reaction. They are fully characterized by FTIR、1H NMR、31P NMR、ESI-MS and EA. For the 6,7-dihydroxy coumarin, there was selective phosphorylation in the 6-hydroxyl group in the reaction. XRD analysis of 2f is described. The crystal is nomoclinic, space group P2(1)/n. there is hydrogen-bonding interaction between O atom on P=O and H atom on O-H.展开更多
Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite （DIPPH） by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of th...Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite （DIPPH） by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of the coumarins in the Atherton-Todd reaction were studied.展开更多
H-phosphonates were conveniently prepared by direct transesterification of diphenyl phosphite (DPP) with the corresponding alcohols, without further purification they were reacted with branched peptide methyl ester (L...H-phosphonates were conveniently prepared by direct transesterification of diphenyl phosphite (DPP) with the corresponding alcohols, without further purification they were reacted with branched peptide methyl ester (L-Leu2-L-LysOMe) through Atherton-Todd method, a series of different substituted alkyloxy (N-phosphoryl-L-Leu)2-L-LvsOMe were synthesized, and their structures were confirmed by P NMR, ESI-MS, H NMR,13 C NMR, IR and elemental analysis. 31 1 The approach possesses the advantages of easy operation, high yield and inexpensive phosphorylating reagent.展开更多
文摘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.
文摘Six kinds of phosphorylated coumarins are successfully synthesized by an Atherton-Todd reaction. They are fully characterized by FTIR、1H NMR、31P NMR、ESI-MS and EA. For the 6,7-dihydroxy coumarin, there was selective phosphorylation in the 6-hydroxyl group in the reaction. XRD analysis of 2f is described. The crystal is nomoclinic, space group P2(1)/n. there is hydrogen-bonding interaction between O atom on P=O and H atom on O-H.
基金The authors thank the financial supports from the National Natural Science Foundation of China(No.20132020)the Ministry of Science and Technology,the Chinese Ministry of Education and Zhengzhou University.
文摘Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite （DIPPH） by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of the coumarins in the Atherton-Todd reaction were studied.
基金The authors would like to thank the financial supports from the National Natural Science Foundation of China(No.20132020)the Ministry of Science and Technology.the Chinese Ministry of Education and Tsinghua University.
文摘H-phosphonates were conveniently prepared by direct transesterification of diphenyl phosphite (DPP) with the corresponding alcohols, without further purification they were reacted with branched peptide methyl ester (L-Leu2-L-LysOMe) through Atherton-Todd method, a series of different substituted alkyloxy (N-phosphoryl-L-Leu)2-L-LvsOMe were synthesized, and their structures were confirmed by P NMR, ESI-MS, H NMR,13 C NMR, IR and elemental analysis. 31 1 The approach possesses the advantages of easy operation, high yield and inexpensive phosphorylating reagent.
