1667-11-4Relevant articles and documents
Multiple-photon ? chemistry in the laser-jet: Photochemistry of the 4-biphenylmethyl radical
Adam, Waldemar,Schneider, Katrin
, p. 441 - 444 (1997)
In laser-jet (LJ) photolysis (high intensity) of the ether 4-(4-benzoylphenoxymethyl)biphenyl 1 a two-photon process is observed in CCl4 to yield 4-(chloromethyl)biphenyl 5 as product (3%), while the one-photon product is 4-biphenylaldehyde 7 (100% in conventional photolysis versus 97% in laser-jet photolysis). In ethanol, the results suggest a three-proton reaction in which 4-(ethoxymethyl)biphenyl 6 is produced in appreciable amounts (18%) in addition to the one-photon product 1,2-bis(4-biphenyl)ethane 4, the latter as the major product (82%). It is proposed that under high-intensity LJ photolysis conditions the electronically-excited 4-biphenylmethyl radical 2* is photoionized to the 4-biphenylmethyl cation 2+ and that the latter is trapped by ethanol to give the 4-biphenylmethyl ether 6.
Mechanism of solvolysis of substituted benzyl chlorides in aqueous ethanol
Denegri, Bernard,Mati?, Mirela,Va?ko, Monika
supporting information, (2021/11/22)
The mechanism of solvolyses of activated ortho-, meta- and para-substituted benzyl chlorides in aqueous ethanol has been studied by using the Hammett-Brown and Yukawa-Tsuno treatments as well as by correlating logarithms of solvolysis rate constants with relative stabilities of corresponding benzyl carbocations in water calculated at the IEFPCM-M06–2X/6-311+G(3df,3pd) level of theory. Benzyl chlorides containing strong conjugative electron-donors in the para-position solvolyze by the SN1 mechanism, whereas other activated benzyl chlorides solvolyze by the SN2 mechanism via loose transition states.
Synthesis and evaluation of tetrahydroisoquinoline derivatives against Trypanosoma brucei rhodesiense
Cullen, Danica R.,Gallagher, Ashlee,Duncan, Caitlin L.,Pengon, Jutharat,Rattanajak, Roonglawan,Chaplin, Jason,Gunosewoyo, Hendra,Kamchonwongpaisan, Sumalee,Payne, Alan,Mocerino, Mauro
, (2021/10/07)
Human African Trypanosomiasis (HAT) is a neglected tropical disease caused by the parasitic protozoan Trypanosoma brucei (T. b.), and affects communities in sub-Saharan Africa. Previously, analogues of a tetrahydroisoquinoline scaffold were reported as having in vitro activity (IC50 = 0.25–70.5 μM) against T. b. rhodesiense. In this study the synthesis and antitrypanosomal activity of 80 compounds based around a core tetrahydroisoquinoline scaffold are reported. A detailed structure activity relationship was revealed, and five derivatives (two of which have been previously reported) with inhibition of T. b. rhodesiense growth in the sub-micromolar range were identified. Four of these (3c, 12b, 17b and 26a) were also found to have good selectivity over mammalian cells (SI > 50). Calculated logD values and preliminary ADME studies predict that these compounds are likely to have good absorption and metabolic stability, with the ability to passively permeate the blood brain barrier. This makes them excellent leads for a blood-brain barrier permeable antitrypanosomal scaffold.
Nickel-Catalyzed Asymmetric Reductive Arylbenzylation of Unactivated Alkenes
Jin, Youxiang,Yang, Haobo,Wang, Chuan
supporting information, p. 2724 - 2729 (2020/04/02)
Herein, we report a nickel-catalyzed asymmetric two-component reductive dicarbofunctionalization of aryl iodide-tethered unactivated alkenes using benzyl chlorides as the challenging coupling partner. This arylbenzylation reaction enables the efficient synthesis of diverse benzene-fused cyclic compounds bearing a quaternary stereocenter with a high tolerance of sensitive functionalities in highly enantioselective manner. The preliminary mechanistic investigations suggest a radical chain reaction mechanism.