Microwave‐Assisted 1,3‐Dioxa‐[3,3]‐Sigmatropic Rearrangement of Substituted Allylic Carbamates: Application to the Synthesis of Novel 1,3‐Oxazine‐2,4‐dione Derivatives

In a first instance, the effect of the microwave irradiation on the 1,3‐Dioxa‐[3,3]‐sigmatropic rearrangement of aryl allylic carbamates was investigated. Under these new conditions, the reaction acceleration was clearly highlighted compared to conventional heating conditions. Depending on the elect...

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Bibliographic Details
Published in:European journal of organic chemistry 2022-01, Vol.2022 (1), p.n/a
Main Authors: Bou Zeid, Samar, Eid, Samar, Najjar, Fadia, Macé, Aurélie, Rivilla, Ivan, Cossío, Fernando P., Dorcet, Vincent, Roisnel, Thierry, Carreaux, François
Format: Article
Language:English
Subjects:
Acceleration
Adducts
Allylic compounds
Aromatic compounds
Carbamates (tradename)
Chemical Sciences
Heterocycles
Microwave
Organic chemistry
Reaction mechanisms
Reaction time
Sigmatropic rearrangement
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Summary:In a first instance, the effect of the microwave irradiation on the 1,3‐Dioxa‐[3,3]‐sigmatropic rearrangement of aryl allylic carbamates was investigated. Under these new conditions, the reaction acceleration was clearly highlighted compared to conventional heating conditions. Depending on the electronic nature of substituents on the aromatic group, this type of rearrangement can be faster with similar or improved yields. Due to this experimental improvement, the diversity of aryl allylic carbamates able to undergo this rearrangement in a reasonable reaction time (30 min.) and with acceptable to high yields was greatly extended. Finally, an original synthetic way involving this microwave‐assisted process to access new six‐membered heterocyclic structures such as (E)‐5‐arylidene‐1,3‐oxazinane‐2,4‐diones was developed from Morita‐Baylis‐Hillman (MBH) adducts showing the interest of this molecular rearrangement approach. DFT and Fragment Distortion studies showed in general polar transition structures and connected high deformation and interaction energies with lower activation barriers. The acceleration of 1,3‐dioxa‐[3,3]‐sigmatropic rearrangement of aryl allylic carbamates under microwave irradiation was described. The implementation of these unconventional thermal conditions allowed the development of an original synthetic route to new heterocycle products such as (E)‐5‐arylidene‐1,3‐oxaninane‐2,4‐diones.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202101100