1634-11-3Relevant articles and documents
SN2 Reaction of Diarylmethyl Anions at Secondary Alkyl and Cycloalkyl Carbons
Shinohara, Riku,Ogawa, Narihito,Kawashima, Hidehisa,Wada, Kyohei,Saito, Shun,Yamazaki, Takashi,Kobayashi, Yuichi
, p. 1461 - 1478 (2019/01/25)
The substitution reaction of the diethyl allylic and propargylic phosphates with Ar2CH anions was applied to sec-alkyl phosphates to compare reactivity and stereoselectivity. However, the substitution took place on the ethyl carbon of the diethyl phosphate group. We then found that the diphenyl phosphate leaving group ((PhO)2PO2) was suited for the substitution at the sec-alkyl carbon. Enantioenriched diphenyl sec-alkyl phosphates with different substituents (Me, Et, iPr) on the vicinal position underwent the substitution reaction with almost complete inversion (>99% enantiospecificity). The substitution reactions of cyclohexyl phosphates possessing cis or trans substituents (Me and/or tBu) at the C4, C3, and C2 positions of the cyclohexane ring were also studied to observe the difference in reactivity among the cis and trans isomers. A transition-state model with the phosphate leaving group ((PhO)2PO2) in the axial position was proposed to explain the difference. This model was supported by computational calculation of the virtual substitution reaction of the structurally simpler “dimethyl” cyclohexyl phosphates (leaving group = (MeO)2PO2) with MeLi. Furthermore, the calculation unexpectedly indicated higher propensity of (PhO)2PO2 as a leaving reactivity than alkyl phosphate groups such as (MeO)2PO2 and (iPrO)2PO2.
Formation of cyclopropanes by homolytic substitution reactions of 3- iodopropyl radicals: Preparative and rate studies
Curran, Dennis P.,Gabarda, Ana E.
, p. 3327 - 3336 (2007/10/03)
Reduction of 2-substituted 1,3-diiodopropane derivatives with tin hydride provides substituted cyclopropanes. The reaction occurs through a homolytic substitution of the 3-iodopropyl radical, which has a rate constant of about 5 x 105 s-1 at 80°C.
Decarbonylative diarylation reaction of N-tosylated α-amino acids
Seong, Mi Ra,Lee, Hong Jung,Kim, Jae Nyoung
, p. 6219 - 6222 (2007/10/03)
The reaction of various N-tosylated α-amino acids with arenes in the presence of sulfuric acid afforded the corresponding diarylated derivatives in moderate yields, which were generated via decarbonylative arylation followed by Friedel-Crafts reaction of the generated tosylamide derivatives.