32341-91-6Relevant articles and documents
Reductive activation and hydrofunctionalization of olefins by multiphoton tandem photoredox catalysis
Czyz, Milena L.,Taylor, Mitchell S.,Horngren, Tyra H.,Polyzos, Anastasios
, p. 5472 - 5480 (2021/06/01)
The conversion of olefin feedstocks to architecturally complex alkanes represents an important strategy in the expedient generation of valuable molecules for the chemical and life sciences. Synthetic approaches are reliant on the electrophilic activation of unactivated olefins, necessitating functionalization with nucleophiles. However, the reductive functionalization of unactivated and less activated olefins with electrophiles remains an ongoing challenge in synthetic chemistry. Here, we report the nucleophilic activation of inert styrenes through a photoinduced direct single electron reduction to the corresponding nucleophilic radical anion. Central to this approach is the multiphoton tandem photoredox cycle of the iridium photocatalyst [Ir(ppy)2(dtbbpy)] PF6, which triggers in situ formation of a high-energy photoreductant that selectively reduces styrene olefinic π bonds to radical anions without stoichiometric reductants or dissolving metals. This mild strategy enables the chemoselective reduction and hydrofunctionalization of styrenes to furnish valuable alkane and tertiary alcohol derivatives. Mechanistic studies support the formation of a styrene olefinic radical anion intermediate and a Birch-type reduction involving two sequential single electron transfers. Overall, this complementary mode of olefin activation achieves the hydrofunctionalization of less activated alkenes with electrophiles, adding value to abundant olefins as valuable building blocks in modern synthetic protocols.
Bisoxazoline-pincer ligated cobalt-catalyzed hydrogenation of alkenes
Ritz, Mikhaila D.,Parsons, Astrid M.,Palermo, Philip N.,Jones, William D.
supporting information, (2020/02/13)
The efficient and atom economical hydrogenation of alkenes using a novel bisoxazoline ligated cobalt complex has been developed. The hydrogenation of a variety of alkenes containing electron neutral and electron-donating groups proceeds in high yield, whi
Benzylation of arenes with benzyl halides synergistically promoted by in situ generated superacid boron trifluoride monohydrate and tetrahaloboric acid
Huang, Ruofeng,Zhang, Xiaohui,Pan, Jing,Li, Jiaqiang,Shen, Hang,Ling, Xuege,Xiong, Yan
supporting information, p. 1540 - 1546 (2015/03/04)
To examine the assembly methodology of diarylmethanes, a benzylation of (hetero)arenes with benzyl halides has been developed and various diarylmethanes were furnished with yields of up to 98% and regioselectivities of up to >99%. The complexation of the by-product halogen hydride with BF3·OEt2 generated the Bronsted acid BF3·HX (HBF3X, X=Cl or Br) in situ to synergistically promote the benzylation.
