Hydrogen Transfer Reactions: Reductions and Beyond

Articles in Focus

Enjoy free access to selected articles from our recently completed topical collections.

Article 1: Hydrogen-Atom Transfer Reactions

by Liang Wang, Jian Xiao

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.

Article 2: C-Alkylation by Hydrogen Autotransfer Reactions

by Yasushi Obora

The development of practical, efficient, and atom-economical methods for the formation of carbon–carbon bonds remains a topic of considerable interest in current synthetic organic chemistry. In this review, we have summarized selected topics from the recent literature with particular emphasis on C-alkylation processes involving hydrogen transfer using alcohols as alkylation reagents. This review includes selected highlights concerning recent progress towards the modification of catalytic systems for the α-alkylation of ketones, nitriles, and esters. Furthermore, we have devoted a significant portion of this review to the methylation of ketones, alcohols, and indoles using methanol. Lastly, we have also documented recent advances in β-alkylation methods involving the dimerization of alcohols (Guerbet reaction), as well as new developments in C-alkylation methods based on sp 3 C–H activation.

Read all articles in this topical collection

Guest Editors:

© SpringerGabriela Guillena

Química Orgánica, Facultad de Ciencias, Universidad de Alicante
Gabriela Guillena was born in Alicante (Spain) in 1970 and received her BSc from the University of Alicante in 1993. After a one-year stay with D. Seebach at the ETH Zurich (Switzerland), she returned to Alicante to complete her MSc (1995) and PhD (2000). She then spent two years as a postdoctoral fellow with G. van Koten (University of Utrecht, The Netherlands) before returning to the University of Alicante, where she was appointed Assistant Professor in 2003. Her research is focused on new methodologies on sustainable organometallic chemistry and asymmetric organic organocatalysis.

© SpringerDiego J. Ramón

Química Orgánica, Facultad de Ciencias, Universidad de Alicante

Diego J. Ramón was born in Alicante (Spain) in 1965, and received his BSc (1988), MSc (1989) and PhD (1993) degrees from the University of Alicante. After spending two years as a postdoctoral fellow at the Eidgenössische Technische Hochschule in Zürich (ETH-Zentrum) he returned to the University of Alicante and, after a short stay at Miguel Hernández University, became associate professor (2000) in the former university, being promoted to full professor in 2010 at the same university. Dr. Ramón has been visiting professor at Debye Institute (University of Utrecht, Netherlands, 2001). In 1994, he was awarded the Prize for Young Scientists of the Spanish Royal Society of Chemistry. His current research interest is focused on organometallic chemistry and asymmetric synthesis. Web page: http://personal.ua.es/en/djramon/research-group-of-diego-j-ramon.html