Catalytic asymmetric functionalization of aromatic C-H bonds by electrophilic trapping of metal-carbene-induced zwitterionic intermediates

Angewandte Chemie
Shikun JiaWen-Hao Hu

Abstract

Asymmetric functionalization of aromatic C-H bonds of N,N-disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α-diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This Rh(II)/chiral phosphoric acid cocatalyzed transformation is proposed to proceed through a metal-carbene-induced zwitterionic intermediate which undergoes electrophilic trapping. To the best of our knowledge, this is the first asymmetric example of metal carbene-induced intermolecular functionalization of aryl C-H bonds.

References

Jul 1, 1973·Journal of Medicinal Chemistry·R A StokbroekxP A Janssen
Jul 10, 2001·The Journal of Organic Chemistry·M YangP Livant
Nov 1, 2001·Journal of the American Chemical Society·C A MerlicM M Miller
Aug 14, 2003·Chemical Reviews·Huw M L Davies, Rohan E J Beckwith
Mar 17, 2004·Angewandte Chemie·Takahiko AkiyamaKohei Fuchibe
Apr 29, 2004·Journal of the American Chemical Society·Daisuke Uraguchi, Masahiro Terada
May 21, 2004·Organic Letters·Huw M L Davies, Qihui Jin
Jul 23, 2005·Angewandte Chemie·Manuel R FructosPedro J Pérez
Nov 7, 2007·Chemical Reviews·Takahiko Akiyama
Dec 13, 2007·Chemical Reviews·Abigail G Doyle, Eric N Jacobsen
Jan 17, 2008·Chemical Society Reviews·Jorge M M VerkadeFloris P J T Rutjes
Jan 25, 2008·Nature·Huw M L Davies, James R Manning
Aug 14, 2008·Chemical Reviews·M Mar Díaz-Requejo, Pedro J Pérez
Aug 20, 2009·Chemical Society Reviews·Zhihui Shao, Hongbin Zhang
Sep 30, 2009·Chemical Reviews·Michael P DoyleLei Zhou
Dec 23, 2009·Journal of the American Chemical Society·Yajing Lian, Huw M L Davies
Oct 1, 1947·Journal of the American Chemical Society·E M SCHULTZJ M SPRAGUE
Apr 30, 2010·Nature Chemistry·Justin T MohrBrian M Stoltz
Jan 27, 2011·Journal of the American Chemical Society·Andrew DeAngelisJoseph M Fox
Feb 12, 2011·The Journal of Organic Chemistry·Luis Simón, Jonathan M Goodman
May 11, 2011·Journal of the American Chemical Society·Jun JiangWen-Hao Hu
Aug 7, 2012·Journal of the American Chemical Society·Wai-Wing ChanWing-Yiu Yu
Aug 14, 2012·Angewandte Chemie·Junichiro YamaguchiKenichiro Itami
Aug 24, 2012·Nature Chemistry·Huang QiuWen-Hao Hu
Nov 17, 2012·Chemical Society Reviews·Zhenting Du, Zhihui Shao
Apr 4, 2013·Journal of the American Chemical Society·Todd K HysterTomislav Rovis
Jul 31, 2013·Journal of the American Chemical Society·Zhuangzhi ShiFrank Glorius
Nov 20, 2013·Accounts of Chemical Research·Xin Guo, Wen-Hao Hu

Citations

Aug 19, 2015·Chemical Reviews·Alan FordM Anthony McKervey
Jun 30, 2015·Journal of the American Chemical Society·Bin XuQi-Lin Zhou
Oct 21, 2016·Journal of the American Chemical Society·Shogo OkumuraYoshiaki Nakao
Jan 13, 2017·Organic Letters·Shogo Okumura, Yoshiaki Nakao
Apr 16, 2016·Angewandte Chemie·Daniel SoléIsrael Fernández
Jun 18, 2017·Journal of the American Chemical Society·Durga Prasad Hari, Jérôme Waser
Nov 23, 2016·Chemistry : a European Journal·Sam G MossJoseph B Sweeney
Feb 22, 2017·Chemical Communications : Chem Comm·Chaoqun MaWenhao Hu
Jan 5, 2017·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Dan Zhang, Wen-Hao Hu
Mar 24, 2018·Nature Communications·Chunchen YuanYingsheng Zhao
Nov 20, 2016·Angewandte Chemie·Miguel Peña-López, Matthias Beller
Jul 1, 2015·Organic & Biomolecular Chemistry·Suleman M InamdarNitin T Patil
Oct 26, 2018·Chemical Communications : Chem Comm·Gopi Krishna Reddy AlavalaWen-Hao Hu
Nov 9, 2019·Organic & Biomolecular Chemistry·Taoda ShiWen-Hao Hu
Mar 19, 2020·Chemistry : a European Journal·Guillaume PisellaJérôme Waser
Nov 17, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Ana CaballeroPedro J Pérez

Related Concepts

Carbene, 13C-labeled
Catalysis
Methane
Rhodium
Molecular Stereochemistry
Aniline Compounds
Arylsulfonates
Hydrocarbons, Aromatic
Imines
Metals

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.

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.

Lipidomics & Rhinovirus Infection

Lipidomics can be used to examine the lipid species involved with pathogenic conditions, such as viral associated inflammation. Discovered the latest research on Lipidomics & Rhinovirus Infection.

Alzheimer's Disease: MS4A

Variants within the membrane-spanning 4-domains subfamily A (MS4A) gene cluster have recently been implicated in Alzheimer's disease in genome-wide association studies. Here is the latest research on Alzheimer's disease and MS4A.

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.

Torsion Dystonia

Torsion dystonia is a movement disorder characterized by loss of control of voluntary movements appearing as sustained muscle contractions and/or abnormal postures. Here is the latest research.

Generating Insulin-Secreting Cells

Reprogramming cells or using induced pluripotent stem cells to generate insulin-secreting cells has significant therapeutic implications for diabetics. Here is the latest research on generation of insulin-secreting cells.

Central Pontine Myelinolysis

Central Pontine Myelinolysis is a neurologic disorder caused most frequently by rapid correction of hyponatremia and is characterized by demyelination that affects the central portion of the base of the pons. Here is the latest research on this disease.

Epigenome Editing

Epigenome editing is the directed modification of epigenetic marks on chromatin at specified loci. This tool has many applications in research as well as in the clinic. Find the latest research on epigenome editing here.