Allenes for Versatile Iron-Catalyzed C-H Activation by Weak O-Coordination: Mechanistic Insights by Kinetics, Intermediate Isolation, and Computation

Journal of the American Chemical Society
Antonis M MessinisLutz Ackermann

Abstract

The iron-catalyzed hydroarylation of allenes was accomplished by weak phenone assistance. The C-H activation proceeded with excellent efficacy and high ortho-regioselectivity in proximity to the weakly coordinating carbonyl group for a range of substituted phenones and allenes. Detailed mechanistic studies, including the isolation of key intermediates, the structural characterization of an iron-metallacycle, and kinetic analysis, allowed the sound elucidation of a plausible catalytic working mode. This mechanistic rationale is supported by detailed computational density functional theory studies, which fully address multi-spin-state reactivity. Furthermore, in operando nuclear magnetic resonance monitoring of the catalytic reaction provided detailed insights into the mode of action of the iron-catalyzed C-H alkylation with allenes.

References

Apr 11, 2000·Accounts of Chemical Research·D SchröderH Schwarz
Dec 26, 2001·Chemical Reviews·R ZimmerF A Khan
Mar 3, 2004·Angewandte Chemie·Anja Hoffmann-Röder, Norbert Krause
Dec 9, 2004·Chemical Reviews·Carsten BolmLorenzo Zani
Jul 14, 2005·Chemical Reviews·Shengming Ma
Apr 16, 2008·Journal of the American Chemical Society·Jakob NorinderEiichi Nakamura
May 24, 2008·Chemical Society Reviews·Arkaitz CorreaCarsten Bolm
Jan 19, 2010·Chemical Reviews·Thomas W Lyons, Melanie S Sanford
Jun 5, 2010·The Journal of Organic Chemistry·Eiichi Nakamura, Naohiko Yoshikai
Nov 6, 2010·Chemical Reviews·Chang-Liang SunZhang-Jie Shi
Mar 11, 2011·Chemical Society Reviews·Lindsay McMurrayMatthew J Gaunt
Mar 26, 2011·Chemical Communications : Chem Comm·Kathrin JungeMatthias Beller
Apr 9, 2011·Journal of the American Chemical Society·Arimasa MatsumotoEiichi Nakamura
Apr 29, 2011·Journal of the American Chemical Society·Laurean IliesEiichi Nakamura
Jan 25, 2012·Angewandte Chemie·Shichao Yu, Shengming Ma
Apr 20, 2012·Angewandte Chemie·Honggen Wang, Frank Glorius
May 30, 2012·Journal of the American Chemical Society·Rong ZengShengming Ma
Jan 5, 2013·Journal of the American Chemical Society·Baihua Ye, Nicolai Cramer
Nov 14, 2013·Journal of the American Chemical Society·Rong ZengShengming Ma
Mar 1, 2014·Accounts of Chemical Research·Ke Gao, Naohiko Yoshikai
Mar 14, 2014·Chemistry : a European Journal·Xiao-Feng XiaYong-Min Liang
Aug 2, 2014·Journal of the American Chemical Society·Erin R FrucheySilas P Cook
Aug 5, 2014·Angewandte Chemie·Brendan M MonksSilas P Cook
Sep 18, 2014·The Journal of Organic Chemistry·Aleix RodríguezErnesto Nicolás
Mar 10, 2015·Chemical Reviews·Ingmar Bauer, Hans-Joachim Knölker
Mar 11, 2015·Accounts of Chemical Research·Olafs DaugulisLy Dieu Tran
Apr 29, 2015·Accounts of Chemical Research·Robin B Bedford
May 13, 2015·Accounts of Chemical Research·Evan P JacksonJohn Montgomery
Jun 30, 2015·Chemical Reviews·Angeles FarránRobert J Linhardt
Aug 8, 2015·Nature Communications·Shangze WuShengming Ma
Aug 12, 2015·Angewandte Chemie·J Philipp Wagner, Peter R Schreiner
Aug 19, 2015·Journal of the American Chemical Society·Donna G Blackmond
Sep 18, 2015·Chemistry : a European Journal·Sachiyo Nakanowatari, Lutz Ackermann
Jun 14, 2016·ACS Central Science·John F Hartwig, Matthew A Larsen
Aug 18, 2016·Angewandte Chemie·Ksenia S Egorova, Valentine P Ananikov
Aug 31, 2016·Topics in Current Chemistry·Junichiro YamaguchiKenichiro Itami
Aug 31, 2016·Topics in Current Chemistry·Gianpiero Cera, Lutz Ackermann
Sep 2, 2016·Angewandte Chemie·Neetipalli ThrimurtuluChandra M R Volla

❮ Previous
Next ❯

Citations

Mar 4, 2021·ACS Central Science·Toryn DaltonFrank Glorius
Mar 18, 2021·Journal of the American Chemical Society·Naoki KimuraFumitoshi Kakiuchi
Aug 14, 2021·Beilstein Journal of Organic Chemistry·Renato L CarvalhoEufrânio N da Silva Júnior
Jul 30, 2021·Chemistry : a European Journal·Srimanta MannaJan-E Bäckvall

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.