1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies

1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies

An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This...

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Veröffentlicht in:Journal of organic chemistry 2018-12, Vol.83 (24), p.14861-14881
Hauptverfasser: Agirre, Maddalen, Henrion, Sylvain, Rivilla, Ivan, Miranda, José I, Cossío, Fernando P, Carboni, Bertrand, Villalgordo, José M, Carreaux, François
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Organic chemistry
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container_end_page 14881
container_issue 24
container_start_page 14861
container_title Journal of organic chemistry
container_volume 83
creator Agirre, Maddalen
Henrion, Sylvain
Rivilla, Ivan
Miranda, José I
Cossío, Fernando P
Carboni, Bertrand
Villalgordo, José M
Carreaux, François
description An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This metal-free tandem reaction from branched allyl alcohols initiated by a carbamoylation reaction and followed by a sigmatropic rearrangement thus offers a new access to (E)-cinnamyl and conjugated (E,E)-diene carbamates, such as N-acyl and N-sulfonyl derivatives. A computational study was conducted in order to rationalize this phenomenon, and a rearrangement progress kinetic analysis was performed.
doi_str_mv 10.1021/acs.joc.8b01320
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title 1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies
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