14159-54-7Relevant articles and documents
Superacid-catalyzed reactions of olefinic pyrazines: An example of anti-markovnikov addition involving superelectrophiles
Zhang, Yiliang,Briski, Jason,Zhang, Yun,Rendy, Rendy,Klumpp, Douglas A.
, p. 2505 - 2508 (2005)
(Chemical Equation Presented) Olefinic pyrazines are found to react with benzene in CF3SO3H and give anti-Markovnikov-type addition products. We propose that this is caused by two effects: destabilization of the carbocationic interme
C2-selective alkylation of pyridines by rhodium–aluminum complexes
Aso, Koki,Hara, Naofumi,Li, Qiao-Zhi,Nakao, Yoshiaki,Sakaki, Shigeyoshi
supporting information, (2021/08/06)
A C2- and mono-selective alkylation of various pyridines and azines with unactivated alkenes and vinylarenes using a heterobimetallic Rh–Al catalyst is reported. The use of aliphatic alkenes exclusively affords the linear alkylation products, while vinylarenes mainly afford branched alkylation products. The details of the reaction mechanism are revealed by DFT calculations: the reductive elimination of the products is rate-determining, which is consistent with the experimental results. The origin of the linear/branched selectivity is elucidated based on deformation/interaction analysis.
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.
