7360-39-6Relevant articles and documents
Reductive Coupling between C-N and C-O Electrophiles
He, Rong-De,Li, Chun-Ling,Pan, Qiu-Quan,Guo, Peng,Liu, Xue-Yuan,Shu, Xing-Zhong
supporting information, p. 12481 - 12486 (2019/09/04)
The cross-electrophile reaction is a promising strategy for C-C bond formation. Recent studies have focused mainly on reactions with organic halides. Here we report a coupling reaction between C-N and C-O electrophiles that demonstrates the possibility of constructing a C-C bond via C-N and C-O cleavage. Several reactions between benzyl/aryl ammonium salts and vinyl/aryl C-O electrophiles have been studied. Preliminary mechanistic studies revealed that the benzyl ammoniums were activated through a radical mechanism.
Elimination-addition mechanism for nucleophilic substitution reaction of cyclohexenyl iodonium salts and regioselectivity of nucleophilic addition to the cyclohexyne intermediate
Fujita, Morifumi,Kim, Wan Hyeok,Sakanishi, Yuichi,Fujiwara, Koji,Hirayama, Sayaka,Okuyama, Tadashi,Ohki, Yasuhiro,Tatsumi, Kazuyuki,Yoshioka, Yasunori
, p. 7548 - 7558 (2007/10/03)
The reaction of 4-substituted cyclohex-1-enyl(phenyl)iodonium tetrafluoroborate with tetrabutyl-ammonium acetate gives both the ipso and cine acetate-substitution products in aprotic solvents. The isomeric 5-substituted iodonium salt also gives the same mixture of the isomeric acetate products. The reaction is best explained by an elimination-addition mechanism with 4-substituted cyclohexyne as a common intermediate. The cyclohexyne formation was confirmed by deuterium labeling and trapping to lead to [4 + 2] cycloadducts and a platinum-cyclohexyne complex. Cyclohexyne can also be generated in the presence of some other mild bases such as fluoride ion, alkoxides, and amines, though amines are less effective bases for the elimination. Kinetic deuterium isotope effects show that the anionic bases induce the E2 elimination (k H/kD > 2), while the amines allow formation of a cyclohexenyl cation in chloroform to lead to E1 as well as SN1 reactions (k H/kD ≈ 1). Bases are much less effective in methanol, and methoxide was the only base to efficiently afford the cyclohexyne intermediate. Nucleophiles react with the cyclohexyne to give regioisomeric products in the ratio dependent on the ring substituent. The observed regioselectivity of nucleophilic addition to substituted cyclohexynes is rationalized from calculated LUMO populations, which are governed by the bond angles at the acetylenic carbons: The less deformed carbon has a higher LUMO population and is preferentially attacked by the nucleophile.
Cyclohexynes. Generation from iodonium salts and regioselective reaction with nucleophile
Fujita, Morifumi,Sakanishi, Yuichi,Kim, Wan Hyeok,Okuyama, Tadashi
, p. 908 - 909 (2007/10/03)
Cyclohexynes are effectively generated by treatment of cyclohex-1-enyliodonium salts with a mild base such as acetate and fluoride ion in chloroform. Regioselectivity of the nucleophilic addition of acetate ion to cyclohexynes depends on the 4-substituent
Selective O-acylation of silyl enol ethers with acid halides mediated by a copper(I) salt
Ito, Hajime,Ishizuka, Tomoko,Tateiwa, Jun-Ichi,Hosomi, Akira
, p. 6295 - 6298 (2007/10/03)
A new selective synthetic method of enol esters (O-acylated products) from silyl enol ether and acid chloride in the presence of CuCl is described. This reaction proceeds smoothly in DMI (1,3-dimethyl-2-imidazolidinone) but not in a less polar solvent. The silicon-copper exchange reaction pathway is proposed for this transformation as in the cases of D and alkynylsilane which were previously reported.
