Zirconoarylation of alkynes through p-chloranil-promoted reductive elimination of arylzirconates

• Xiaoyu Yan,
• Chao Chen and
• Chanjuan Xi

Beilstein J. Org. Chem. 2014, 10, 528–534, doi:10.3762/bjoc.10.48

• reaction can afford multi-substituted olefins with high stereoselectivity. Keywords: alkyne; multicomponent; reductive elimination; zirconate; zirconoarylation; Introduction The controlled synthesis of multi-substituted olefins is one of the most challenging tasks in organic synthesis [1][2]. A series of

• to fulfill arylzirconation of alkynes (Scheme 2). Recently, we have reported a p-chloranil (TCQ)-promoted reductive elimination reaction of the zirconate complex Li[Cp2Zr(C≡CR)3] toward geminal enediynes [44]. As part of our ongoing project on organozirconate chemistry [45][46][47][48], we envisioned

• aryllithium compounds were coupled in one-pot in the presence of Cp2Zr species to afford highly substituted 1,3-butadienes. The pathway of the oxidation of zirconate 2 to vinylzirconocene 4 is not yet clear. A possible mechanism is proposed in Scheme 6. Coordination of TCQ to zirconium results in reductive