Open AccessSynthesis of Oxygenated ortho-Methylbenzaldehydes via Aryne [2+2] Cycloaddition and Benzocyclobutenol Ring Opening
Author(s) -
Mark M. Maturi,
Ken Ohmori,
Keisuke Suzuki
Publication year - 2018
Publication title -
chimia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.387
H-Index - 55
eISSN - 2673-2424
pISSN - 0009-4293
DOI - 10.2533/chimia.2018.870
Subject(s) - aryne , chemistry , cycloaddition , regioselectivity , ring (chemistry) , methanol , benzene , acetaldehyde , lithium (medication) , medicinal chemistry , organic chemistry , combinatorial chemistry , catalysis , ethanol , endocrinology , medicine
Herein, a two-step procedure for the preparation of oxygenated ortho-methylbenzaldehyde derivatives, starting from commercially available bromoarenes, is described. The synthesis features the simultaneous and highly regioselective installation of both the methyl and the formyl group onto the benzene core via benzyne [2+2] cycloadditions with acetaldehyde lithium enolate to give the corresponding benzocyclobutenols in high yields. Bond-selective ring opening of the benzocyclobutenols under basic conditions in methanol delivers the title compounds.