Prediction on chemoselectivity for selected organocatalytic reactions by the DFT version of the Hückel-defined free valence index

Abstract

Developing reliable indexes for prediction of the actual chemical active site of substrates is one of the most challenging questions in chemistry field. Herein, we suggested a general method for...

Theoretical investigation of a chiral Brønsted acid (CBA)-catalyzed isomerization reaction of BCB: mechanism and origin of stereoselectivity

“…Thus, we consider identifying key factors that govern the stereoselectivity to be interesting and informative. With theoretical investigations of the mechanism of organocatalytic reactions at the core of the research activity in our group, 8 we now performed a theoretical investigation of the mechanism of CBA-catalyzed activation/transformation of BCB using the DFT method, which has frequently used for mechanistic investigations of organocatalytic 9 and organometallic reactions. 10…”

Diels–Alder cycloadditions of fullerene: Advances in mechanistic theory

“…24 The DA reaction provides a reliable method to obtain sixmembered rings with good regio-and stereoselectivity, which is a powerful and popular tool for derivatizing fullerene. 25,26 Consequently, understanding the DA reaction mechanisms is crucial to the further development of fullerene science. 27,28 The Woodward-Hoffman rule and frontier orbital theory are often used to understand the cycloaddition reactions of fullerene.…”

“…One such transformation is the Diels–Alder ( DA ) reaction, a thermally allowed [4 + 2] cycloaddition with the Woodward–Hoffmann symbol [π4 s + π2 s ] 24 . The DA reaction provides a reliable method to obtain six‐membered rings with good regio‐ and stereoselectivity, which is a powerful and popular tool for derivatizing fullerene 25,26 . Consequently, understanding the DA reaction mechanisms is crucial to the further development of fullerene science 27,28 …”