(Diethylphosphinyl)difluoromethyllithium. — Preparation and synthetic application —

Analogues of nucleotides and oligonucleotides featuring difluorophosphonate, difluorophosphonothioate and difluorophosphinate functional groups

“…The disubstitution of carbon C 3 0 in nucleosides prevented us from using reactant 8a in a SN 2 -type reaction [13]. Instead, a protocol calling for (i) the addition of 8a onto a keto group and (ii) a radical-based deoxygenation of the resultant adduct 9 was considered [14].…”

Aspartyl Phosphonates and Phosphoramidates: The First Synthetic Inhibitors of Bacterial Aspartate-Semialdehyde Dehydrogenase

“…The reaction mixture was treated with anhydrous Na 2 SO 4 and filtered through a pad of Celite, then more diethyl ether was added to wash the Celite layer. Finally all the solvent was evaporated and a transparent oil was obtained (2RS)-Diethyl-[(1,1-difluoro-2-hydroxy-2-phenyl)ethyl] phosphonate (33): [19,36] Diethyl-[difluoro(trimethylsilyl)methyl] phosphonate (125 mL, 96 %, 0.5 mmol) was dissolved in anhydrous THF (2 mL). Benzaldehyde (51 mL, 99 %, 0.5 mmol) was added and the solution was cooled to À 78 8C.…”

“…Mp: 72 ± 75 8C (EtOAc/petroleum ether (40 : 60)), (ref. [36]: 76 ± 77 8C); IR (solid): n Ä max 3324 (OÀH), 3011 (CÀH aromatic), 2988 (CÀH), 2914 (CÀH), 1250 (PO), 1037 (PÀOÀalkyl), 1008 (CÀF) cm À1 ; 1 …”

New Prospects toward the Synthesis of Difluoromethylated Phosphate Mimics

“…The reported access to the difluoromethylphosphonate motif focused on five main retrosynthetic disconnections. First, the venerable Arbuzov [15] or Michaelis-Becker [16] reactions were used to synthesize this key scaffold. The electrophilic fluorination of alkyl phospho- nates, initially developed by Differding, [17] represented an elegant alternative pathway to the widely used deoxyfluorination reaction of keto-phosphates by means of DAST or other fluorinating agents.…”