The last several years have seen an explosion of new reagents and methodologies for the synthesis of oligophosphorylated molecules, due to their prevalence in biological systems. This field has slowly developed since Khorana's pioneering first synthesis of adenosine triphosphate (ATP) in 1954, and an improved synthesis of ATP and of other nucleoside triphosphate (NTP) derivatives has been a major area of focus in synthetic oligophosphorylation. Many of the recent developments have focused on reagents for the simultaneous addition of three phosphate units, via trimetaphosphate ((P 3 O 9 ) 3-, TriMP) in order to minimize the number of synthetic steps to convert a nucleoside into an NTP. The first effective TriMP based methodology was that of Taylor, utilizing the activation of TriMP with sulfonyl chloride reagents. These seminal papers have been followed up more recently with our own group's 1 as well as Jessen's isolable triphosphorylation reagents. By utilizing substrates B. X-ray crystal structure of 1 with thermal ellipsoids set at 50% probability and cations omitted (red for oxygen, orange for phosphorus, yellow for sulfur, grey for carbon). C. X-ray crystal structure of 3 with thermal ellipsoids set at 50% probability and cations omitted (red for oxygen, orange for phosphorus, blue for nitrogen, grey for carbon).