118736-07-5Relevant articles and documents
A Sterically Congested α-Cyanoamine as a Cyanating Reagent: Cyanation of Acetals and Orthoesters
Kotani, Shunsuke,Sakamoto, Midori,Osakama, Kazuki,Nakajima, Makoto
supporting information, p. 6606 - 6609 (2015/10/29)
The cyanation of acetals and orthoesters by using a sterically congested α-cyanoamine as a cyanating reagent was investigated. The α-cyanoamine effectively facilitated cyanation in the presence of trichlorosilyl triflate to produce a variety of cyanated adducts in excellent yields. Analysis of the reaction mixture by 1H NMR spectroscopy revealed that trichlorosilyl triflate produced an oxocarbenium cation species as an intermediate.
Effects of phosphorus substituents on reactions of α- alkoxyphosphonium salts with nucleophiles
Goto, Akihiro,Otake, Kazuki,Kubo, Ozora,Sawama, Yoshinari,Maegawa, Tomohiro,Fujioka, Hiromichi
, p. 11423 - 11432 (2012/11/07)
The effects of phosphorus substituents on the reactivity of α-alkoxyphosphonium salts with nucleophiles has been explored. Reactions of α-alkoxyphosphonium salts, prepared from various acetals and tris(o-tolyl)phosphine, with a variety of nucleophiles proceeded efficiently. These processes represent the first examples of high-yielding nucleophilic substitution reactions of α-alkoxyphosphonium salts. The reactivity of these salts was determined by a balance between steric and electronic factors, respectively, represented by cone angles θ and CO stretching frequencies ν (steric and electronic parameters, respectively). In addition, a novel reaction of α-alkoxyphosphonium salts derived from Ph3P with Grignard reagents was observed to take place in the presence of O2 to afford alcohols in good yields. A radical mechanism is proposed for this process that has gained support from isotope-labeling and radical-inhibition experiments. A dramatic change in the reactivity of an α-alkoxyphosphonium salt toward nucleophiles is observed due to the steric and electronic nature of the phosphine substituents. By changing the type of phosphorus substituents, the reaction pathway can be controlled to proceed selectively by substitution or a new radical reaction (see scheme; OTf=trifluoromethansulfonate, TMS=trimethylsilyl, o-tol=tolyl). Copyright
Photolysis of Triarylacetonitriles. A Novel Photochemical Generation of Phenyl(cyano)carbene
Shi, Min,Okamoto, Yoshiki,Takamuku, Setsuo
, p. 1044 - 1054 (2007/10/02)
Upon UV irradiation in methanol, triarylacetonitrile underwent a novel α,α-elimination of two aryl groups to give biaryl and α-methoxyarylacetonitrile.However, when a methoxy group was introduced into the phenyl group, another photochemical process which gave the corresponding triarylmethane and methoxytriarylmethane as major products took place simultaneously.
