Fig. 5: Rearrangement of ultraphosphates.
a Analytical results for trisadenosine ultraphosphate (21) [PPN] salt after 14 days in DMF: 1H-31P-HMBC with two cross-peaks for internally modified oligophosphates. CE-MS analysis of the product mixture and proposed structures 65 and 66 for the internally modified compounds. b Phosphate walk rearrangement for trisadenosine ultraphosphate (21) and nucleophilic attack of the linearised product 66. c Possible mechanistic pathways of the phosphate walk rearrangement for trimethyl ultraphosphate dihydrate (67). Mechanistic studies were carried out at the B97D/Def2-TZVPD(water) level of theory; for details see Supplementary Note 9.2.
