Tetrabutylammonium Nitrate

Organic Nitrating Reagents

“…In addition, TBAN is a commercially available and inexpensive substance available in large quantities (~10 g/$50). 179 191…”

Hirao Cross-Coupling Reaction as an Efficient Tool to Build Non-natural C2-Phosphonylated Sugars

“…5 Moreover, the glycochemist toolbox has grown significantly in recent decades and provided elegant ways to build non-natural glycosidic bonds. While the literature focuses on the anomeric position, the development of an efficient synthesis of the bench-stable 2-iodoglycal building blocks by Vankar et al in 2014, 6 paved the way for a wide diversity of C2-glyco-analogues through the use of metal-catalyzed cross-couplings. Standard cross-coupling reactivities such as Suzuki–Miyaura, Sonogashira or Heck reactions have been successfully applied on these scaffolds in addition to several examples of carbonylative processes.…”

“…The investigation of the Hirao reactivity on 2-iodoglycals was performed on compound 1a (Table 1 ), obtained by iodination of the commercial 3,4,6-tri-OAc- d -glucal according to Vankar’s conditions. 6 Compound 1a was reacted with a small excess of diethylphosphite in the presence of Pd(OAc) 2 as the catalyst, XPhos as the ligand, and DIPEA as the base in a mixture of t BuOH/EtOH at 110 °C overnight (entry 1). These initial conditions allowed the desired product 2a to be formed in a low yield of 21% ( 1 H NMR analysis).…”

“…Compounds 2-iodo-3,4,6-tri- O -acetyl- d -glucal, 2-iodo-3,4,6-tri- O -benzyl- d -glucal, 2-iodo-3,4,6-tri- O -benzyl- d -galactal, 2-iodo-3,4-di- O -acetyl- l -rhamnal, 2-iodo-3,6-di- O -acetyl-4- O -(2,3,4,6-tetra- O -acetyl-β- d -galactopyranosyl)- d -glucal were prepared according to the literature: 6 7m the corresponding glycal was dissolved in anhydrous acetonitrile (8 mL/mmol) under argon, and the resulting mixture was heated to 80 °C. At this temperature, N -iodosuccinimide (1.2 equiv) and silver nitrate (20 mol %) were added.…”

“…2-Iodo-3,4,6-tri- O - para -methoxybenzyl- d -glucal was prepared by following the literature procedure: 6 3,4,6-Tri- O - para -methoxybenzyl- d -glucal (2.236 g, 1 equiv, 4.41 mmol) was dissolved in anhydrous acetonitrile (35 mL) under argon, and the resulting mixture was heated to 80 °C. At this temperature, N -iodosuccinimide (1.192 g, 1.2 equiv, 5.30 mmol) and silver nitrate (150 mg, 0.2 equiv, 0.88 mmol) were added, and the resulting mixture was stirred at 80 °C for 2 h. The mixture was filtrated on Celite with EtOAc, and concentrated with silica.…”