Depending on the reactant property and reaction mechanism, one major regioisomer can be favored in areaction that involves multiple active sites.H erein, an orthogonal regulation of nucleophilic and electrophilic sites in the regiodivergent hydroamination of isoprene with indazoles is demonstrated. Under Pd-hydride catalysis,t he 1,2-or 4,3insertion pathway with respect to the electrophilic sites on isoprene could be controlled by the choice of ligands.Interms of the nucleophilic sites on indazoles,t he reaction occurs at either the N 1-o rN 2-position of indazoles is governed by the acid co-catalysts.P reliminary experimental studies have been performed to rationalizet he mechanism and regioselectivity. This study not only contributes ap ractical tool for selective functionalization of isoprene,b ut also provides ag uide to manipulate the regioselectivity for the N-functionalization of indazoles.
Terpenes, consisting of isoprene monomer units, represent a family of naturally abundant compounds. The difunctionalization of terpenes is highly appealing yet remains challenging, since the multiple unbiased C]C bonds of terpenes lead to difficulty in controlling the regioselectivity. Herein, a cobalt(III)-catalyzed C-H activation strategy has been developed to facilitate hydroxymethylarylation of terpenes with formaldehyde and arenes with high chemo-and regio-selectivities. These (chemo-and regio-) selectivities are governed by the coordination abilities of isoprene, directing groups and the steric effect. This terpene difunctionalization also features high atom and step economy through a C-H addition pathway. Scheme 1 Representative homoallylic alcohols and their derivatives in nature. ; Web: [http://www.lbcs.dicp.ac.cn] † Electronic supplementary information (ESI) available. See rsc.li/chemical-science 9560 | Chem. Sci., 2019, 10, 9560-9564 This journal is
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