Experimental and Semiempirical Calculation Studies of Transannular Diels-Alder and Other Competing Pericyclic Reactions

1995 ◽  
Vol 117 (1) ◽  
pp. 518-529 ◽  
Author(s):  
Yves L. Dory ◽  
Pierre Soucy ◽  
Marc Drouin ◽  
Pierre Deslongchamps
Keyword(s):  
Diels Alder ◽  
Semiempirical Calculation ◽  
Pericyclic Reactions

ChemInform Abstract: Synthesis of Cyclic Alkenes by Pericyclic Reactions: Diels-Alder Reactions

ChemInform ◽  
2012 ◽  
Vol 43 (28) ◽  
pp. no-no
Author(s):  
F. Fringuelli ◽  
O. Piermatti ◽  
F. Pizzo ◽  
L. Vaccaro
Keyword(s):  
Diels Alder ◽  
Pericyclic Reactions ◽  
Cyclic Alkenes

Cyclic Alkyne Approach to Heteroatom-Containing Polycyclic Aromatic Hydrocarbon Scaffolds

2019 ◽  
Author(s):  
Evan Darzi ◽  
Joyann Barber ◽  
Neil Garg
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbons ◽  
Diels Alder ◽  
Pericyclic Reactions ◽  
One Pot ◽  
Synthetic Strategy ◽  
Polycyclic Aromatic

We report a modular synthetic strategy for accessing heteroatom-containing polycyclic aromatic hydrocarbons (PAHs) that relies on the controlled generation of transient heterocyclic alkynes and arynes. The strained intermediates undergo in situ trapping with readily accessible oxadiazinones. Four sequential pericyclic reactions occur, namely two Diels–Alder / retro-Diels–Alder sequences, which can be performed in a stepwise or one-pot fashion to assemble four new carbon–carbon (C–C) bonds.

Porphyrins and other pyrrolic macrocycles in cycloaddition reactions

2009 ◽  
Vol 13 (04n05) ◽  
pp. 408-414 ◽  
Author(s):  
Augusto C. Tomé ◽  
Maria G.P.M.S. Neves ◽  
José A.S. Cavaleiro
Keyword(s):  
Diels Alder ◽  
Cycloaddition Reactions ◽  
Pericyclic Reactions ◽  
Dipolar Cycloadditions

Porphyrins and other pyrrolic macrocycles can participate in a range of pericyclic reactions. This review deals mainly with their use in Diels-Alder reactions (as dienes and dienophiles) and in 1,3-dipolar cycloadditions (as 1,3-dipoles and dipolarophiles)

The versatile reactivity of 2-aryl-4,6-dinitrobenzotriazole 1-oxides in Diels-Alder type condensations and in σ-complexation - A relationship between superelectrophilicity and pericyclic reactivity

2001 ◽  
Vol 79 (11) ◽  
pp. 1617-1623 ◽  
Author(s):  
Dominique Vichard ◽  
Taoufik Boubaker ◽  
François Terrier ◽  
Marie-José Pouet ◽  
Julian M Dust ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Direct Relationship ◽  
Diels Alder ◽  
Pericyclic Reactions ◽  
Oxide Structure ◽  
Oxide Substrates ◽  
Thermodynamic Measurements ◽  
Inverse Demand ◽  
Electrophilic Reactivity ◽  
Trans Addition

A two-pronged study of a series of 2-aryl-4,6-dinitrobenzotriazole 1-oxide substrates (2a–c) is reported: Diels–Alder type pericyclic reactivity and covalent hydration to yield Meisenheimer type hydroxy anionic σ-adducts. The most activated benzotriazole 1-oxide 2a is found to exhibit both dienophilic and heterodienic behaviour on treatment with cyclopentadiene, providing a highly functionalized stereoselective diadduct (7). This diadduct is shown to be the result of two consecutive inverse demand Diels–Alder condensations proceeding through the endo mode with a trans addition of two cyclopentadiene molecules. Kinetic and thermodynamic measurements of the ease of covalent hydration of 2a–c to give σ-adducts 4a–c in aqueous solution indicate that the electrophilic reactivity of the 4,6-dinitrobenzotriazole 1-oxide structure is much closer to that of the superelectrophilic 4,6-dinitrobenzofuroxan (DNBF, 1a) than that of the standard Meisenheimer electrophile 1,3,5-trinitrobenzene (TNB). The pKa values range from 6.70 for the 2-(2',4',6'-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide (Pi-DNBT, 2a) to 10.73 for the 2-phenyl-4,6-dinitrobenzotriazole 1-oxide (Ph-DNBT, 2c). The observation that the most activated benzotriazole 1-oxide structure 2a which resembles 4,6-dinitrobenzofuroxan (DNBF) in superelectrophilic behaviour, is the only one that undergoes Diels–Alder reactions, points to a direct relationship between superelectrophilic and pericyclic reactivity.Key words: σ-complexes, arylnitrobenzotriazole 1-oxides, super-electrophiles, Diels–Alder condensations, pericyclic reactions.

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