CHAPTER 4: Recent Advances in Designed Local Electric Fields

Remote designed local electric fields (D-LEFs) are emerging as a practical strategy for the manipulation of chemical reactivity. This chapter surveys the historical use of D-LEFs, and explores the theory and practical use of Brønsted acids and bases, metal ions, and ion-pairs as novel effectors of D-LEFs, with key concepts such as polarisation illustrated using recent theoretical and experimental case studies. Particular attention is paid to the use of D-LEFs in concert with existing catalysts and catalytic strategies, within photochemistry and excited states, and in the manipulation of regio- and diastereoselectivity. Prospective advances in the efficient use of D-LEFs are also surveyed, and the need for further experimental validation of D-LEF effects is emphasised.