50585-08-5Relevant 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.
Modern Friedel-Crafts chemistry. Part-271. Alkylation of benzene with 1-benzyl- and 1-phenylcyclohexanols in the presence of H 2SO4 and AlCl3/CH3NO2 catalysts
Khalaf, Ali A.,Awad, Ibrahim M.,El-Emary, Talaat I.,Abd El-Aal, Hassan A. K.
, p. 1018 - 1022 (2007/10/03)
The alkylation of benzyene with 1-benzylcyclohexanol (3) gave a mixture of 2,3-benzobicyclo[3.3.1]nona-2-ene (8, 79%) and cyclohexyldiphenylmethane (10, 21%) with AlCl3/CH3NO2 catalyst and a mixture of 1-benzylcyclohexene 5 (47.5%), 8 (8%), 10 (21.5%), 1-cyclopentyl-1,2- diphenylethane (12, 18%) and 1-benzyl-1-phenylcyclohexene (13, 4%) with H 2SO4 catalyst. Treatment of 3 with AlCl 3/CH3NO2 in petroleum ether gave a mixture of 5 (26%) and 8 (62%). Attempted alkylation of benzene with 1-phenylcyclohexanol (4) in the presence of either AlCl3/CH3NO2 or H2SO4 catalyst gave 1-(1-phenylcyclohexyl)-2- phenylcyclohexene (17) as sole product. Mechanistic interpretation of the results in terms of carbocation behaviour is offered.
A new class of chiral organogermanes derived from C2-symmetric dithiols: Synthesis, characterization and stereoselective free radical reactions
Gualtieri, Giovanna,Geib, Steven J.,Curran, Dennis P.
, p. 5013 - 5019 (2007/10/03)
A new class of dithiostannanes and dithiogermanes have been prepared from 1,1′-binaphthyl-2,2′-dithiol and 3,3′-bis(trimethylsilyl)-1,1′ -binaphtho-2,2′-dithiol. While reduction of 4-butyl-4-chloro-3,5-dithia-4-stanna-cyclohepta[2,1-a;3,4- a′]dinaphthalen