2785-88-8Relevant academic research and scientific papers
Regioselectivity of Cobalamin-Dependent Methyltransferase Can Be Tuned by Reaction Conditions and Substrate
Pompei, Simona,Grimm, Christopher,Farnberger, Judith E.,Schober, Lukas,Kroutil, Wolfgang
, p. 5977 - 5983 (2020/10/06)
Regioselective reactions represent a significant challenge for organic chemistry. Here the regioselective methylation of a single hydroxy group of 4-substituted catechols was investigated employing the cobalamin-dependent methyltransferase from Desulfitobacterium hafniense. Catechols substituted in position four were methylated either in meta- or para-position to the substituent depending whether the substituent was polar or apolar. While the biocatalytic cobalamin dependent methylation was meta-selective with 4-substituted catechols bearing hydrophilic groups, it was para-selective for hydrophobic substituents. Furthermore, the presence of water miscible co-solvents had a clear improving influence, whereby THF turned out to enable the formation of a single regioisomer in selected cases. Finally, it was found that also the pH led to an enhancement of regioselectivity for the cases investigated.
A Mild meta-Selective C–H Alkylation of Catechol Mono-Ethers
Vitaku, Edon,Njardarson, Jon T.
, p. 3679 - 3683 (2016/08/16)
Catechol mono-ethers are an important class of phenols. They are found in a number of pharmaceuticals, flavoring agents, perfumes, and are used for the preparation of numerous drugs. Herein, we report a mild meta-selective C–H alkylation of these phenols, which is enabled by a cascade of oxidative dearomatization – radical addition – rearomatization process. The method is compatible with reactive functional groups on the parent arenol, such as olefins and halides. Primary, secondary, and teriary alkyl groups can be used, the source of which is most commonly an alkylborane. This process is operationally simple, does not require heating and generally proceeds in good yields.
Sodium Bis(trimethylsily)amide and Lithium Diisopropylamide in Deprotection of Alkyl Aryl Ethers: α-Effect of Silicon
Hwu, Jih Ru,Wong, Fung Fuh,Huang, Jiann-Jyh,Tsay, Shwu-Chen
, p. 4097 - 4104 (2007/10/03)
Removal of methyl, benzyl, and methylene groups from alkyl aryl ethers is among the most popular deprotecting methods in organic synthesis. Alkali organoamides NaN(SiMe3)2 and LiN(i-Pr)2, often used as organic bases, have been developed as efficient deprotecting agents. Treatment of aryl methyl ethers with 1.5 equiv of NaN(SiMe3)2 or LiN(i-Pr)2 in THF and 1,3-dimethyl-2-imidazolidinone in a sealed tube at 185 °C produced the corresponding phenol derivatives in good to excellent yields (80-97percent). Removal of the methylene unit from benzodioxole derivatives was also accomplished by use of 2.5 equiv of these alkali organoamides. The corresponding catechols were obtained in 93-99percent yields. The activity of NaN(SiMe3)2 was proven lower than that of LiN(i-Pr)2; it is due to the steric congestion and the α-stabilizing effect of the silyl groups. Thus selective mono-O-demethylation of o-dimethoxybenzenes can be achieved by the use of NaN(SiMe3)2 but not LiN(i-Pr)2. O-Debenzylation of aryl benzyl ethers, however, can be accomplished by the use of LiN(i-Pr)2.
Tobacco smoke chemistry. 2. Alkyl and alkenyl substituted guaiacols found in cigarette smoke condensate.
Arnarp,Bielawski,Dahlin,Dahlman,Enzell,Pettersson
, p. 44 - 50 (2007/10/02)
A series of alkyl and alkenyl substituted guaiacols, which comprise a group of biologically and organoleptically active compounds, have been synthesized. Mass spectra and GC retention times for these have been recorded and compared with those obtained for constituents of a weakly acidic fraction of smoke condensate derived from American blend type cigarettes. On the basis of these results, 25 guaiacols have been identified, 18 of which have not been detected in tobacco smoke condensate previously.
