597-96-6Relevant articles and documents
Palladium-Catalyzed C(sp3)?H Arylation of Primary Amines Using a Catalytic Alkyl Acetal to Form a Transient Directing Group
St John-Campbell, Sahra,Ou, Alex K.,Bull, James A.
supporting information, p. 17838 - 17843 (2018/11/23)
C?H Functionalization of amines is a prominent challenge due to the strong complexation of amines to transition metal catalysts, and therefore typically requires derivatization at nitrogen with a directing group. Transient directing groups (TDGs) permit C?H functionalization in a single operation, without needing these additional steps for directing group installation and removal. Here we report a palladium catalyzed γ-C?H arylation of amines using catalytic amounts of alkyl acetals as transient activators (e.g. commercially available (2,2-dimethoxyethoxy)benzene). This simple additive enables arylation of amines with a wide range of aryl iodides. Key structural features of the novel TDG are examined, demonstrating an important role for the masked carbonyl and ether functionalities. Detailed kinetic (RPKA) and mechanistic investigations determine the order in all reagents, and identify cyclopalladation as the turnover limiting step. Finally, the discovery of an unprecedented off-cycle free-amine directed ?-cyclopalladation of the arylation product is reported.
Study of syntheses and specific rotations of (S)-3-phenylhexan-3-ol and its derivatives
Liao, Tou-Gen,Ren, Jie,Fan, Hua-Fang,Xie, Ming-Jin,Zhu, Hua-Jie
, p. 808 - 815 (2008/09/21)
Tertiary alcohols, 3-phenylhexan-3-ol and 3-methylhexane-3-ol, and their derivatives were synthesized. The reaction conditions of the esterification of the tertiary alcohol with 2-NO2PhCO2Cl and 4-NO2PhCO2Cl were optimized. The absolute configuration of the derivative from (S)-3-phenylhexan-3-ol was identified by X-ray study and computational methods. Experimental results confirmed the computational specific rotation predictions by DFT-based and matrix methods.
Alkane oxygenation with H2O2 catalysed by FeCl 3 and 2,2′-bipyridine
Shul'pin, Georgiy B.,Golfeto, Camilla C.,Süss-Fink, Georg,Shul'pina, Lidia S.,Mandelli, Dalmo
, p. 4563 - 4567 (2007/10/03)
The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60°C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide.