scholarly journals Investigating radical cation chain processes in the electrocatalytic Diels–Alder reaction

2018 ◽  
Vol 14 ◽  
pp. 642-647 ◽  
Author(s):  
Yasushi Imada ◽  
Yohei Okada ◽  
Kazuhiro Chiba
Keyword(s):  
Radical Cation ◽  
Catalytic Efficiency ◽  
Alder Reaction ◽  
Diels Alder ◽  
High Current Efficiency ◽  
Induction Periods ◽  
Chain Processes ◽  
Rate Determining Step ◽  
Diels Alder Reaction ◽  
Scalable Synthesis

Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels–Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

Ab Initio Studies of the Radical Cation Diels−Alder Reaction

1999 ◽  
Vol 121 (28) ◽  
pp. 6730-6736 ◽  
Author(s):  
Udo Haberl ◽  
Olaf Wiest ◽  
Eberhard Steckhan
Keyword(s):  
Ab Initio ◽  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

scholarly journals The Intramolecular Radical Cation Induced Diels-Alder Reaction in the Diene - Diene Format

Molecules ◽  
1997 ◽  
Vol 2 (12) ◽  
pp. 80-86 ◽  
Author(s):  
David Rusterholz ◽  
David Gorman ◽  
Paul Gassman
Keyword(s):  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Mass-Spectra of Annelated 4H-3,1-Oxazin-4-ones

1989 ◽  
Vol 42 (10) ◽  
pp. 1813 ◽  
Author(s):  
LK Dyall
Keyword(s):  
Electron Impact ◽  
Radical Cation ◽  
Mass Spectra ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Impact Fragmentation

Electron-impact fragmentation of 2-R-4H-3,1-benzoxazin-4-ones involves primary losses of CO2 and R; there is also loss of ketene when R is methyl. The ion RCO+ is a major daughter. Successive losses of CO2and RCN yield an ion m/z 76 formulated as dehydrobenzene radical cation. In the case of 2-methyl-4H-3,1-naphth[2,3-d]oxazin-4-one, the 2,3-dehydronaphthalene ion is produced efficiently, and linked scans (B/E) were used to demonstrate that it loses C4H2 ( diacetylene ) in a retro Diels-Alder reaction.

Green-light-driven thioxanthylium-based organophotoredox catalysts: Organophotoredox promoted radical cation Diels-Alder reaction

2018 ◽  
Vol 59 (36) ◽  
pp. 3361-3364 ◽  
Author(s):  
Kenta Tanaka ◽  
Mami Kishimoto ◽  
Mayumi Sukekawa ◽  
Yujiro Hoshino ◽  
Kiyoshi Honda
Keyword(s):  
Radical Cation ◽  
Green Light ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

ChemInform Abstract: Photochemically Induced Radical Cation Diels-Alder Reaction of Indole and Electron-Rich Dienes.

ChemInform ◽  
2010 ◽  
Vol 22 (29) ◽  
pp. no-no
Author(s):  
A. W. GIESELER ◽  
E. STECKHAN ◽  
O. WIEST ◽  
F. KNOCH
Keyword(s):  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

scholarly journals Exo-selective intermolecular Diels–Alder reaction by PyrI4 and AbnU on non-natural substrates

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Rajnandani Kashyap ◽  
Naga Veera Yerra ◽  
Joachyutharayalu Oja ◽  
Sandeepchowdary Bala ◽  
Gal Reddy Potuganti ◽  
...  
Keyword(s):  
Organic Chemistry ◽  
Catalytic Efficiency ◽  
Alder Reaction ◽  
Diels Alder ◽  
Fluorescence Studies ◽  
Diels Alder Reaction

AbstractThe 100-year-old Diels–Alder reaction (DAr) is an atom economic and elegant organic chemistry transformation combining a 1,3-diene and a dienophile in a [4+2] cycloaddition leading to a set of products with several stereo centres and multiple stereoisomers. Stereoselective [4+2] cycloaddition is a challenge. Here, we describe two natural enzymes, PyrI4 and AbnU performing stereospecific intermolecular DAr on non-natural substrates. AbnU catalyses a single exo-stereoisomer by 32-fold higher than the background. PyrI4 catalyses the same stereoisomer (15-fold higher) as a major component (>50%). Structural, biochemical and fluorescence studies indicate that the dienophile enters first into the β-barrel of the enzymes followed by the 1,3-diene, yielding a stereospecific product. However, if some critical interactions are disrupted to increase the catalytic efficiency, stereoselectivity is compromised. Since it is established that natural enzymes can carry out intermolecular DAr on non-natural substrates, several hundreds of Diels-Alderases available in nature could be explored.

Gas-phase Diels-Alder reaction of the o-quinodimethane radical cation and neutral styrene

1983 ◽  
Vol 48 (9) ◽  
pp. 1522-1527 ◽  
Author(s):  
Edward K. Chess ◽  
Ping Huang Lin ◽  
Michael L. Gross
Keyword(s):  
Gas Phase ◽  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Formal synthesis of kingianin A based upon a novel electrochemically-induced radical cation Diels–Alder reaction

2014 ◽  
Vol 50 (83) ◽  
pp. 12523-12525 ◽  
Author(s):  
Jonathan C. Moore ◽  
E. Stephen Davies ◽  
Darren A. Walsh ◽  
Pallavi Sharma ◽  
John E. Moses
Keyword(s):  
Natural Product ◽  
Radical Cation ◽  
Alder Reaction ◽  
Diels Alder ◽  
Natural Product Synthesis ◽  
Electrochemical Reactions ◽  
Formal Synthesis ◽  
Diels Alder Reaction

The application of electrochemical reactions in natural product synthesis has burgeoned in recent years. We herein report a formal synthesis of the complex and dimeric natural product kingianin A, which employs an electrochemically-mediated radical cation Diels–Alder cycloaddition as the key step.

Sign in / Sign up

Export Citation Format

Share Document