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In contrast, stable dienes, such as naphthalene, require forcing conditions and/or highly reactive dienophiles, such as N-phenylmaleimide. Anthracene , being less aromatic (and therefore more reactive for Diels–Alder syntheses) in its central ring can form a 9,10 adduct with maleic anhydride at 80 °C and even with acetylene , a weak ...
The imine is often generated in situ from an amine and formaldehyde.An example is the reaction of cyclopentadiene with benzylamine to an aza norbornene. [9]The catalytic cycle starts with the reactions of the aromatic amine with formaldehyde to the imine and the reaction of the ketone with proline to the diene.
Intramolecular Diels–Alder (IMDA) reactions pair tethered dienes and dienophiles in a [4+2] fashion, the most common being terminal substitution. These transformations are popular in total synthesis and have seen a wide spread use in advance to numerous difficult synthetic targets. [6]
Other common classes of dienes are oxo- and aza- butadienes. [9] [11] The key quality of a good DA INV diene is a significantly lowered HOMO and LUMO, as compared to standard DA dienes. Below is a table showing a few commonly used DA INV dienes, their HOMO and LUMO energies, and some standard DA dienes, along with their respective MO energies.
The Diels–Alder reaction with 1,3-dienes gives 1,4-cyclohexadienes. This general reaction has been extensively developed. Electrophilic alkynes are especially effective dienophiles. The "cycloadduct" derived from the addition of alkynes to 2-pyrone eliminates carbon dioxide to give the aromatic compound.
Release of nitrogen from six-membered, cyclic diazenes is common and often spontaneous at room temperature. Such a reaction can be utilized in click reactions where alkanes react with a 1,2,4,5-tetrazine in a diels alder then retro diels alder reaction with the loss of nitrogen. In this another example, the epoxide shown undergoes rDA at 0 °C.
In the presence of very reactive dienes (for example 1,3-diphenylisobenzofuran) butadienesulfone behaves as a dienophile and forms the corresponding Diels-Alder adduct. [ 21 ] As early as 1938, Kurt Alder and co-workers reported Diels-Alder adducts from the isomeric 2-sulfolene with 1,3-butadiene and 2-sulfolene with cyclopentadiene .
Cyclic and acyclic dienes generally give cyclobutanones, rather than Diels-Alder adducts. In reactions of cyclic dienes, the larger ketene substituent is placed in the endo position. [11] Fulvenes typically react in the ring, leaving the double bond intact. [12] (6) Ketenes undergo [2+2] cycloaddition with ketones and aldehydes to give β-lactones.