16170-45-9Relevant articles and documents
Pd-Catalyzed Allylic Isocyanation: Nucleophilic N-Terminus Substitution of Ambident Cyanide
Yurino, Taiga,Tani, Ryutaro,Ohkuma, Takeshi
, p. 4434 - 4440 (2019)
In the presence of catalytic amount of Pd(OAc)2, allylic phosphates reacted with trimethylsilyl cyanide (TMSCN) to afford the corresponding allylic isonitriles exclusively. No allylic nitriles, which are selectively obtained in the traditional
From Stoichiometric Reagents to Catalytic Partners: Selenonium Salts as Alkylating Agents for Nucleophilic Displacement Reactions in Water
Martins, Nayara Silva,ángel, Alix Y. Bastidas,Anghinoni, Jo?o M.,Lenard?o, Eder J.,Barcellos, Thiago,Alberto, Eduardo E.
supporting information, p. 87 - 93 (2021/11/03)
The ability of chalcogenium salts to transfer an electrophilic moiety to a given nucleophile is well known. However, up to date, these reagents have been used in stoichiometric quantities, producing a substantial amount of waste as byproducts of the reaction. In this report, we disclose further investigation of selenonium salts as S-adenosyl-L-methionine (SAM) surrogates for the alkylation of nucleophiles in aqueous solutions. Most importantly, we were able to convert the stoichiometric process to a catalytic system employing as little as 10 mol % of selenides to accelerate the reaction between benzyl bromide and other alkylating agents with sodium cyanide in water. Probe experiments including 77Se NMR and HRMS of the reaction mixture have unequivocally shown the presence of the selenonium salt in the reaction mixture. (Figure presented.).
Dual electrocatalysis enables enantioselective hydrocyanation of conjugated alkenes
Song, Lu,Fu, Niankai,Ernst, Brian G.,Lee, Wai Hang,Frederick, Michael O.,DiStasio, Robert A.,Lin, Song
, p. 747 - 754 (2020/07/03)
Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, we address this long-standing synthetic problem using dual electrocatalysis. Using this strategy, we leverage electrochemistry to seamlessly combine two canonical radical reactions—cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation—to accomplish highly enantioselective hydrocyanation without the need for stoichiometric oxidants. We also harness electrochemistry’s unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis uncovers the origin of enantio-induction, for which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions to direct the enantio-determining C–CN bond formation. This work demonstrates the power of electrochemistry in accessing new chemical space and providing solutions to pertinent challenges in synthetic chemistry. [Figure not available: see fulltext.]
