Zirconocene-Based Methods for the Preparation of BN-Indenes : Application to the Synthesis of 1,5-Dibora-4a,8a-diaza-1,2,3,5,6,7-hexaaryl-4,8-dimethyl-s-indacenes
Morgan, M. M., Patrick, E. A., Rautiainen, M., Tuononen, H., Piers, W. E., & Spasyuk, D. M. (2017). Zirconocene-Based Methods for the Preparation of BN-Indenes : Application to the Synthesis of 1,5-Dibora-4a,8a-diaza-1,2,3,5,6,7-hexaaryl-4,8-dimethyl-s-indacenes. Organometallics, 36 (14), 2541-2551. doi:10.1021/acs.organomet.7b00051
DisciplineEpäorgaaninen ja analyyttinen kemia
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
A method for the preparation of 3-bora-9aza-indene heterocycles based on zirconocene mediated functionalization of the ortho-CH bonds of pyridines has been developed and used to make two such compounds. Unlike other methods, the boron center in these heterocycles remains functionalized with a chloride ligand and so the compounds can be further elaborated through halide abstraction and reduction. The utility of the method was further demonstrated by applying it towards the preparation of 1,5- dibora-4a,8a-diaza BN analogues of the intriguing hydrocarbon s-indacene starting from 2,5-dimethylpyrazine. Gram quantities of one such compound was prepared and fully characterized, and both experimental and computational data is presented to compare its properties to those of the parent hydrocarbon s-indacene. These data indicate that the BN substituted derivative exhibits lowered aromaticity in relation to the hydrocarbon.