Exploring the Origin of the Generalized Anomeric Effects in the Acyclic Nonplanar Systems

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2017-07, Vol.121 (29), p.5548-5560
• Main Authors: Hasanzadeh, Neda, Nori-Shargh, Davood, Yahyaei, Hooriye, Mousavi, Seiedeh Negar, Kamrava, Sahar
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.7b04447

Contrary to the published conclusions in the literature concerning the origin of the generalized anomeric relationships in open-chain nonplanar systems, its origin has remained an open question. In order to explore the origin of the generalized anomeric relationships in open-chain nonplanar systems, we assessed the roles and contributions of the effective factors on the conformational properties of methyl propargyl ether (1), methyl propargyl sulfide (2), and methyl propargyl selenide (3) by means of the G3MP2, CCSD­(T), MP2, LC-ωPBE, and B3LYP methods and natural bond orbital (NBO) interpretations. We examined the contributions of the hyperconjugative interactions on the conformational preferences of compounds 1–3 by the deletions of the orbitals overlapping from the Fock matrices of the gauche- and anti-conformations. The trend observed for energy changes in the Fock matrices justify the variations of the gauche-conformations preferences going from compound 1 to compound 3, revealing that the hyperconjugative interactions are solely responsible for the generalized anomeric relationships in compounds 1–3. Accordingly, the conclusions published in the literature concerning the origin of the generalized anomeric effect in the acyclic nonplanar compounds should be revised by these findings. The Pauli exchange type repulsions (PETR) are in favors of the gauche-conformations and the variations of the PETR differences between the gauche- and anti-conformations of compounds 1–3 correlate well with their gauche-conformations preferences, revealing that the generalized anomeric relationships in compounds 1–3 have also the Pauli exchange-type repulsions origin. The resemblance between the preorthogonal natural bond orbitals (that are involved in the hyperconjugative interactions) and their corresponding molecular orbitals have been investigated.