Diboron-promoted iron-catalyzed denitrative vinylation of ß-nitrostyrenes with cycloketoximes.

We have developed a new iron-catalyzed ring opening alkenylation of cycloketoximes with ß-nitrostyrenes for the facile synthesis of flexible distal cyanoalkyl alkenes. Both non-active strained cycloketoximes and less-strained cycloketoximes could be coupled with ß-nitrostyrenes with excellent regio- and stereoselectivity under base-free redox-neutral conditions. The diboron reagent played an irreplaceable role in this transformation. A reasonable radical-mediated process could be involved in this catalytic cycle.

SOMOphilic Alkynylation of Unreactive Alkenes Enabled by Iron-Catalyzed Hydrogen Atom Transfer.

We report an efficient and practical iron-catalyzed hydrogen atom transfer protocol for assembling acetylenic motifs into functional alkenes. Diversities of internal alkynes could be obtained from readily available alkenes and acetylenic sulfones with excellent Markovnikov selectivity. An iron hydride hydrogen atom transfer catalytic cycle was described to clarify the mechanism of this reaction.