Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated Olefins

We reported a Ni(cod)2catalyzed 1,2-dicarbofunctionalization of 2-vinylbenzaldehyde derivatives with aryl halides/triflates and arylzinc reagents.

Roshan K. Dhungana; Shekhar KC; Prakash Basnet; Ramesh Giri

2018

Scholarcy highlights

  • Transition metal-catalyzed difunctionalization of unactivated olefins is a powerful synthetic method that has been scrutinized in organic synthesis over the course of the last few decades
  • An alkyl-TM, represented as C(sp3)- complex 2, is generated as an intermediate after carbometallation of R- derived from the first carbon source C1 onto olefins, which is subsequently intercepted by a second carbon entity C2 during the reaction
  • In 1988, pioneering work from Grigg and coworkers demonstrated such idea in which a C(sp3)-PdX species could be intercepted directly by organotin reagents, without requiring the intervention by CO, to furnish five- and six-membered cyclization/cross-coupling products from olefins tethered to aryl halides
  • In 2001, a seminal work was reported by Oshima and coworkers in which the authors revealed that theCoCl2 catalyst was able to perform a cyclization/cross-coupling of a variety of olefin-tethered alkyl halides with aryl Grignard reagents, a reaction that would proceed via the formation of C(sp3)- species bearing -Hs
  • Mechanistic studies based on ring-opening with cyclopropylmethyl iodide and interception of alkyl groups from alkylzinc reagents with TEMPO in the presence of Ni/pybox catalyst indicated that the reaction could proceed with the generation of alkyl radicals from olefin-tethered alkyl iodides followed by cyclization
  • We recently disclosed a Cu-catalyzed cyclization/cross-coupling of aryl iodides with alkyl- and arylzinc reagents derived from olefin-tethered alkyl and aryl halides. The reaction enabled the synthesis of a variety of cyclopentyl, furanyl, pyrrodinyl, indanyl, dihydrofuranyl and indolinyl cores

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