Abstract
As one of the most important chemical reactions, SN2 reactions play a central role in both synthetic chemistry and the development of mechanistic paradigms. Most of the previous attention has centered on substitution at carbon, whereas displacement at nitrogen is clearly less studied and less understood. The SN2@N reactions have enormous synthetic potential, especially in heterocyclic chemistry, which is a cornerstone of medicinal chemistry, and has been receiving increasing attention, both experimentally and computationally. In this review, we outline the experimental and theoretical studies on the gas-phase SN2 reactions at nitrogen in recent years, and make comprehensive comparisons between gasphase SN2 at carbon and at nitrogen. Some new structure-energy relationships have been proposed. Meanwhile, the similarities and differences of the α-Effect, which refer to the increased nucleophilicity relative to a given basicity for nucleophiles with one or more pairs of unshared electrons adjacent to the attacking atom, between the gas-phase SN2@C and SN2@N reactions are discussed.
Keywords: SN2@C, SN2@N, reactivity of nucleophile, leaving ability.
Graphical Abstract
Call for Papers in Thematic Issues
Catalytic C-H bond activation as a tool for functionalization of heterocycles
The major topic is the functionalization of heterocycles through catalyzed C-H bond activation. The strategies based on C-H activation not only provide straightforward formation of C-C or C-X bonds but, more importantly, allow for the avoidance of pre-functionalization of one or two of the cross-coupling partners. The beneficial impact of ...read more
Related Books
Advances in Organic Synthesis
The Synthetic Methods, Structures, and Properties of the Ca-C σ Bond Organocalcium Containing Compounds
Advances in Organic Synthesis
Chemistry of Bipyrazoles: Synthesis and Applications
Advances in Organic Synthesis
Advanced Nanocatalysis for Organic Synthesis and Electroanalysis
Advances in Organic Synthesis
Advances in Organic Synthesis
37
1
1
1