Intramolecular Nonbonding Interactions between Selenium and Sulfur – Spectroscopic Evidence and Importance in Asymmetric Synthesis

Abstract

Keywords: Asymmetric electrophilic additions / Chiral selenenylating reagents / Noncovalent interactions / Selenium / Sulfur Chiral sulfur-containing electrophilic selenium reagents can be employed to effect efficient asymmetric syntheses. Spectroscopic and chemical evidence demonstrate that the observed high selectivity of the asymmetric reactions is associ-

Intramolecular Nonbonded Interactions Between Divalent Selenium Centers with Donor and Acceptor Substituents

“…It was found that the 77 Se NMR chemical shift (δ Se ) is sensitive to the environment around the Se center, and its shift can be used as a measure of the strength of the nonbonding interactions of Se with other atoms with lone pairs. [24][25][26] To explore whether there are intramolecular nonbonding interactions between the Se centers of 1-3 in solution, first we compared the 77 Se NMR chemical shifts of 1 with the model compounds 12-16 shown in Figure 5. Originally we thought that methyl phenyl selenide (16) (δ Se = 199 ppm) [26] might be a good model for 1.…”

“…[24][25][26] To explore whether there are intramolecular nonbonding interactions between the Se centers of 1-3 in solution, first we compared the 77 Se NMR chemical shifts of 1 with the model compounds 12-16 shown in Figure 5. Originally we thought that methyl phenyl selenide (16) (δ Se = 199 ppm) [26] might be a good model for 1. However, comparison of its δ Se value with that obtained for 12 shows that the latter is better suited for our purpose.…”

Synthesis, X-ray structure and antiproliferative activity of 3-benzylthio-4-propargylselenoquinoline

“…A similar 1,4 short contact between S and Se atoms has been characterized in the structure of 2 with SÁÁÁSe distance of 3.199 Å (Boryczka et al, 2001). The nonbonding selenium-sulfur interaction and its importance in asymmetric synthesis were observed in arylselenenyl halides (Tiecco et al, 2006).…”

The synthesis and crystal structure of 2-(chloroselanyl)pyridine 1-oxide: the first monomeric organoselenenyl chloride stabilized by an intramolecular secondary Se...O interaction

“…The title compound represents the first monomeric organoselenenyl chloride stabilized intramolecularly by an interaction of this type. Previously, the analogous stabilization of monomeric organoselenenyl chlorides by intramolecular secondary SeÁ Á ÁS (Tiecco et al, 2006) and SeÁ Á ÁN (Panda et al, 1999;Klapö tke et al, 2004;Kulcsar et al, 2007;Pö llnitz et al, 2011) interactions have been reported.…”