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oai:riubu.ubu.es:10259/49262021-11-10T09:38:25Zcom_10259_3593com_10259_5086com_10259_2604col_10259_3594

2018-10-06T02:45:06Z urn:hdl:10259/4926 Gold-Catalyzed Synthesis of 1-(Indol-3-yl)carbazoles: Selective 1,2-Alkyl vs 1,2-Vinyl Migration Suárez, Anisley Suarez Pantiga, Samuel Nieto Faza, Olalla . Sanz Díez, Roberto Gold(III)-catalyzed cycloisomerization of α-bis(indol-3-yl)methyl alkynols selectively affords 1-(indol-3-yl)carbazoles, in a transformation that takes place through a selective 1,2-alkyl vs 1,2-vinyl migration step in the vinyl-gold intermediate generated from the initial 5-endo-spirocyclization. The reaction proceeds well with either tertiary or secondary starting alkynols as well as with a wide variety of alkyne substituents. The key role of the other indol-3-yl substituent for the unexpected selectivity in the 1,2 rearrangement has also been supported by DFT calculations that reveal a low barrier, two-step mechanism in the alkyl migration path where the second indole significantly stabilizes a carbocationic intermediate. 2018-09-07T10:56:59Z 2018-10-06T02:45:06Z 2017-10 info:eu-repo/semantics/article 1523-7060 http://hdl.handle.net/10259/4926 10.1021/acs.orglett.7b02303 eng Organic Letters. 2018, V. 19, n. 19, p. 5074–5077 https://doi.org/10.1021/acs.orglett.7b02303 info:eu-repo/grantAgreement/JCyL/BU076U16 info:eu-repo/grantAgreement/MINECO/CTQ2016-75023-C2-1-P info:eu-repo/grantAgreement/MINECO/CTQ2016-75023-C2-2-P info:eu-repo/semantics/openAccess American Chemical Society