DFT studies of the formation of furanoid derivatives of ammonium chlorides

• The DFT studies of reaction of chlorides of THF derivatives with ammonia are shown.
• All the structures were fully optimized in the gas phase, in chloroform and water.
• The calculations revealed the barrier height order is as follows: 1 → 4 < 2 → 5 < 3 → 6.
• MPW1K functional activation barriers are higher than those from B3LYP one.
• The preferred conformations are close to the north (1 → 4, 3 → 6) or south pole (2 → 5).

B3LYP/6-31+G** level computations were performed on the formation of ammonium salts during the reaction of (S)-1,4-anhydro-5-chloro-2,3,5-trideoxypentitol (1) (2S,5S)-2,5-anhydro-6-chloro-1,3,4,6-tetradeoxyhexitol (2) and methyl 5-chloro-2,3,5-trideoxy-β-D-pentofuranoside (3) with ammonia in order to describe the reaction pathway in detail. All the structures were fully optimized in the gas phase, in chloroform and water. In addition, the gas phase activation barrier heights were estimated at B3LYP/6-311++G**, MPWIK/6-31+G**, MPWIK/6-311++G** and MP2/6-311++G(2d,2p)//MPWIK/6-31+G** levels of theory. All the calculations in solvents were performed the using polarizable continuum model (PCM) and the B3LYP functional with the 6-31+G** basis set. A detailed description of all the stationary points is presented, and the conformational behavior of the five-membered ring is discussed in the gas phase and in the solvents. The conversion of the reactant complexes into ion pairs is accompanied by a strong energy decrease in the gas phase and in all the solvents. The overall process is strongly unfavorable in the gas phase, but takes place readily in high-polarity solvents.

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