The stereoselective phosphine-catalyzed ((pMeOC(6)H(4))(3)P, 10-20 mol %) dearomatization of 3-NO2-indoles with allenoates is described. A range of densely functionalized indolines (18 examples) is obtained in high yields (up to 96%) under mild reaction conditions (rt, air, reagent-grade solvent). Computational simulations and labeling experiments revealed a stepwise [3 + 2]-type mechanism involving a water-assisted hydrogen shift and accounted for the diastereoselection recorded.
Phosphine-Catalyzed Stereoselective Dearomatization of 3-NO2-Indoles with Allenoates / Alessandro Cerveri; Olalla Nieto Faza; Carlos Lopez Silva; Stefano Grilli; Magda Monari; Marco Bandini. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1520-6904. - ELETTRONICO. - 84:10(2019), pp. 6347-6355. [10.1021/acs.joc.9b00559]
Phosphine-Catalyzed Stereoselective Dearomatization of 3-NO2-Indoles with Allenoates
Alessandro CerveriMethodology
;Stefano GrilliFormal Analysis
;Magda MonariMethodology
;Marco Bandini
Conceptualization
2019
Abstract
The stereoselective phosphine-catalyzed ((pMeOC(6)H(4))(3)P, 10-20 mol %) dearomatization of 3-NO2-indoles with allenoates is described. A range of densely functionalized indolines (18 examples) is obtained in high yields (up to 96%) under mild reaction conditions (rt, air, reagent-grade solvent). Computational simulations and labeling experiments revealed a stepwise [3 + 2]-type mechanism involving a water-assisted hydrogen shift and accounted for the diastereoselection recorded.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
