Hydrogen-Atom Transfer Reactions

Part of the following topical collections:
  1. Hydrogen Transfer Reactions


The cascade [1,n]-hydrogen transfer/cyclization, recognized as the tert-amino effect one century ago, has received considerable interest in recent decades, and great achievements have been made. With the aid of this strategy, the inert C(sp3)–H bonds can be directly functionalized into C–C, C–N, C–O bonds under catalysis of Lewis acids, Brønsted acids, as well as organocatalysts, and even merely under thermal conditions. Hydrogen can be transferred intramolecularly from hydrogen donor to acceptor in the form of hydride, or proton, followed by cyclization to furnish the cyclic products in processes featuring high atom economy. Methylene/methine adjacent to heteroatoms, e.g., nitrogen, oxygen, sulfur, can be exploited as hydride donor as well as methylene/methine without heteroatom assistance. Miscellaneous electrophilic subunits or intermediates, e.g., alkylidene malonate, carbophilic metal activated alkyne or allene, α,β-unsaturated aldehydes/ketone, saturated aldehydes/iminium, ketenimine/carbodiimide, metal carbenoid, electron-withdrawing groups activated allene/alkyne, in situ generated carbocation, can serve as hydride acceptors. This methodology has shown preeminent power to construct 5-, 6-, or 7-membered heterocyclic as well as carbon rings. In this chapter, various hydrogen donors and acceptors are adequately discussed.


Hydrogen transfer Hydrogen donors Hydrogen acceptors C(sp3)–H functionalization Heterocycles 







Camphorsulfonic acid




Density functional theory




2,4-Dinitrobenzensulfonic acid


Diphenyl phosphate


Electrocyclic ring closure




Hydrogen transfer


O-iodoxybenzoic acid


meta-Chloroperbenzoic acid




Molecular sieves


Protecting group


p-Toluenesulfonic acid


Room temperature




Trifluoroacetic acid




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© Springer International Publishing Switzerland 2016

Authors and Affiliations

  1. 1.College of Chemistry and Pharmaceutical SciencesQingdao Agricultural UniversityQingdaoChina

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