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

被引：9

作者：

Agirre, Maddalen ^{[1
,2
,3
]}

Henrion, Sylvain ^{[5
]}

Rivilla, Ivan ^{[1
,2
,3
]}

Miranda, Jose I. ^{[4
]}

Cossio, Fernando P. ^{[1
,2
,3
]}

Carboni, Bertrand ^{[5
]}

Villalgordo, Jose M. ^{[6
]}

Carreaux, Francois ^{[5
]}

机构：

[1] Univ Basque Country, Euskal Herriko Unibertsitatea UPV EHU, Fac Quim, Dept Quim Organ 1, P Manuel Lardizabal 3, San Sebastian 20018, Spain

[2] Univ Basque Country, Euskal Herriko Unibertsitatea UPV EHU, Fac Quim, Ctr Innovac Quim Avanzada ORFEO CINQA, P Manuel Lardizabal 3, San Sebastian 20018, Spain

[3] DIPC, P Manuel Lardizabal 3, San Sebastian 20018, Spain

[4] Univ Basque Country, Euskal Herriko Unibertsitatea UPV EHU, SGIker NMR Facil, Avda Tolosa 72, E-20018 San Sebastian, Spain

[5] Univ Rennes, CNRS, ISCR, UMR 6226, 263 Ave Gen Leclerc,Campus Beaulieu, F-35000 Rennes, France

[6] Parque Tecnol Fuente Alamo, VillaPharma Res, Av Azul, Murcia 30320, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 24期

关键词：

ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC-SYNTHESIS; CATALYZED SYNTHESIS; GAS-PHASE; SUBSTRATE SCOPE; ALCOHOLS; ESTERS; ISOMERIZATION; RUTHENIUM; AMINATION;

D O I：

10.1021/acs.joc.8b01320

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：14861 / 14881

页数：21

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