An efficient chemical fixation of nitric oxide: convenient and practical synthesis of 1,2,3-oxadiazole 3-oxidesElectronic supplementary information (ESI) available: crystal and molecular structure of 2a. See http://www.rsc.org/suppdata/cc/b3/b311382e/

Abstract

Nitric oxide reacts efficiently with alkynyllithium at low temperature producing 1,2,3-oxadiazole 3-oxides in good yields.

A Computational Study on the Mechanism for the Chemical Fixation of Nitric Oxide Leading to 1,2,3-Oxadiazole 3-oxide

“…The harmonic vibrational frequencies were also calculated at the same level to characterize the nature of the stationary points as true minima with no imaginary or transition states with only one imaginary frequency and to provide thermodynamic quantities such as thermal corrections to energy, enthalpy, and Gibbs free energy. All thermodynamic data reported in this paper were estimated at the experimental temperature of −78 °C and pressure of 1.0 atm as presented in ref . Wiberg bond indices for all stationary points were analyzed using the natural bond orbital (NBO) method .…”

“…As we know, nitric oxide is considered to be an atmospheric pollutant along with NO 2 , mainly leading to acid rain. On the other hand, nitric oxide has attracted increasing attention in the biological and chemical fields. − Many studies have shown that NO has a variety of biological activities including inhibition of platelet aggregation, relaxation of smooth muscle, neurotransmission, 6 and so on. It is also a unique signaling molecule and a biological messenger in biochemical processes.…”

“…It is also a unique signaling molecule and a biological messenger in biochemical processes. 7-11 In addition, nitric oxide is also widely used in chemical synthesis. − Due to the high reactivity of nitric oxide, it is a key component in chemical synthesis for directly fixing nitric oxide into organic molecules in high yield under mild conditions. Recently, Hrabie et al presented a review on reactions of nitric oxide leading to a special atomic grouping of two nitrogen and two oxygen atoms (−N 2 O 2 −).…”

“…Although the chemical fixation of nitric oxide was extensively experimentally investigated in the past decades, a new reaction of nitric oxide with alkynes was not reported until last year. Sugihara et al have investigated the reaction of nitric oxide with various alkynes in a THF solution. The results showed that the yield of product, by using alkynyllithium as the reactant, was dramatically improved and that the reaction was reproducible at −78 °C (Scheme ).…”

Methylation of Sydnone N-Oxides: Kinetic and Thermodynamic Control in the Alkylation Site of an Electron-Rich Heterocycle

“…In particular the N -oxides are remarkably acid and base stable and show little tendency to react with dipolarophiles . They are also unusual diazeniumdiolates as they have an E geometry instead of the almost exclusively observed Z geometry. − Since our initial discovery of 1 , related sydnone N -oxides have been prepared by the addition of nitric oxide to lithiated terminal alkynes . Prior synthetic approaches to sydnones are limited to a single sequence of nitrosation followed by cyclodehydration of 2-aminocarboxylates .…”