Multifunctionality of the N-Trichloroacetyl Group Developed in the Synthesis of Tetrodotoxin, a Puffer Fish Toxin

作者：Nishikawa, Toshio^*; Urabe, Daisuke; Adachi, Masaatsu; Isobe, Minoru

来源：Synlett, 2015, 26(14): 1930-1939.

DOI：10.1055/s-0034-1380781

• protecting groups
• tetrodotoxin
• trichloroacetamide
• neighboring-group effects
• protecting-group transformations

This account describes a serendipitous discovery and the development of unique reactions associated with trichloroacetamide during synthetic studies of tetrodotoxin in our laboratory. The reactions include site-selective hydroxylation using the neighboring-group participation of trichloroacetamide, guanidinylation from a trichloroacetamide, protecting-group transformation, and removal of the N-trichloroacetyl group. These studies indicate the importance of the total synthesis of densely functionalized natural products as a field for the development of new reactions. 1 Introduction 2 Improvement of the Conditions for the Overman Rearrangement to Introduce Trichloroacetamide 3 Site-Selective Hydroxylation Using the Neighboring-Group Participation of Trichloroacetamide 4 Guanidine Synthesis 5 Protecting-Group Transformation of the N-Trichloroacetyl Group 6 New Deprotection Conditions for the Removal of the N-Trichloroacetyl Group 7 Conclusion

• 出版日期2015-9
• 单位中山大学