Reaction Outcome Critically Dependent on the Method of Workup: An Example from the Synthesis of 1-Isoquinolones

0543495 - ÚOCHB 2022 RIV US eng J - Článek v odborném periodiku
Matouš, P. - Májek, M. - Kysilka, O. - Kuneš, J. - Maříková, J. - Růžička, A. - Pour, M. - Kočovský, Pavel
Reaction Outcome Critically Dependent on the Method of Workup: An Example from the Synthesis of 1-Isoquinolones.
Journal of Organic Chemistry. Roč. 86, č. 12 (2021), s. 8078-8088. ISSN 0022-3263. E-ISSN 1520-6904
Institucionální podpora: RVO:61388963
Klíčová slova: chiral bipyridine N,N'-dioxides * asymmetric allylation * enantioselective allylation
Obor OECD: Organic chemistry
Impakt faktor: 4.198, rok: 2021
Způsob publikování: Omezený přístup
https://doi.org/10.1021/acs.joc.1c00561

A striking dependence on the method of workup has been found for annulation of benzonitriles ArC≡N to N-methyl 2-toluamide (1), facilitated by n-BuLi (2 equiv): quenching the reaction by a slow addition of water produced the expected 1-isoquinolones 2, by contrast, slow pouring of the reaction mixture into water afforded the cyclic aminals 5 (retaining the NMe group of the original toluamide). The mechanism of the two processes is discussed in terms of the actual H+ concentration in the workup. Both 2 and 5 were then converted into the corresponding 1-chloroisoquinolines 3, coupling of which, mediated by (Ph3P)2NiCl2/Zn, afforded bis-isoquinolines 4.
Trvalý link: http://hdl.handle.net/11104/0320684