348613-08-1Relevant articles and documents
Directed Remote Lateral Metalation: Highly Substituted 2-Naphthols and BINOLs by In Situ Generation of a Directing Group
Patel, Jignesh J.,Laars, Marju,Gan, Wei,Board, Johnathan,Kitching, Matthew O.,Snieckus, Victor
, p. 9425 - 9429 (2018)
A general synthesis of highly substituted 2-naphthols based on a new carbanionic reaction sequence is demonstrated. The reaction exploits the dual nature of lithium bases consisting of consecutive ring opening of readily available coumarins with either LiNEt2 or LiNiPr2 into Z-cinnamamides, thus generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation for ring closure to give the aryl 2-naphthols in good to excellent yields. These transformations can be combined to provide a more efficient one-pot process. Mechanistic insight into the remote lateral metalation step, demonstrating the requirement of Z-cinnamamide, is described. Application of this methodology to the synthesis of highly substituted 3,3′-diaryl BINOL ligands is also reported.
Synthesis of Unsymmetrical Diaryl Acetamides, Benzofurans, Benzophenones, and Xanthenes by Transition-Metal-Free Oxidative Cross-Coupling of sp3 and sp2 C-H Bonds
Rathore, Vandana,Sattar, Moh.,Kumar, Raushan,Kumar, Sangit
, p. 9206 - 9218 (2016/10/14)
A chemo- and regioselective intermolecular sp3 C-H and sp2 C-H coupling reaction for C-C bond formation is described to access unsymmetrical diaryl acetamides under TM-free conditions from sec- and tert-arylacetamides and nitroarenes using tert-butoxide base in DMSO at room temperature. The coupling partners with sensitive functionalities such as chloro, bromo, hydroxy, and cyano were also amenable to the developed reaction. Synthesized α-(2/4-nitroaryl) phenylacetamides have been transformed into biologically important benzofurans, xanthenes, diaryl indoles, and unsymmetrical benzophenones by novel routes without applying a transition metal. Overall, an economical, yet efficient, strategy has been devised to access unsymmetrical diarylacetamides with the possibility of their further elaboration into a variety of biologically important heterocycles. Mechanistic understanding suggests that the reaction proceeds by a nucleophilic addition of a phenylacetamide carbanion, which is generated in the presence of tert-butoxide base, to the para or ortho (if para is substituted) position of nitrobenzene. The formed α-(4-nitrocyclohexa-2,4-dien-1-yl) phenylacetamide anion intermediate oxidized by a basic solution of DMSO or atmospheric oxygen led to the desired sp3 C-H and sp2 C-H coupled α-(2/4-nitroaryl) phenylacetamides.
A practical in situ generation of the schwartz reagent. reduction of tertiary amides to aldehydes and hydrozirconation
Zhao, Yigang,Snieckus, Victor
supporting information, p. 390 - 393 (2014/04/03)
A new, highly efficient in situ protocol (Cp2ZrCl2/LiAlH(OBu-t)3) is described for the generation of the Schwartz reagent which provides a convenient method for the amide to aldehyde reduction and the regioselective hydrozirconation-iodination of alkynes and alkenes. Highlighted are chemoselective reductions of benzamides derived by directed ortho metalation (DoM) chemistry, allowing the synthesis of valuable 1,2,3-substituted benzaldehydes. The single-step, three-component process proceeds in a very short reaction time, shows excellent functional group compatibility, and uses inexpensive and long-storage stable reducing reagents.
Pd(ii)-catalyzed decarboxylative acylation of phenylacetamides with α-oxocarboxylic acids via C-H bond activation
Park, Jihye,Kim, Minyoung,Sharma, Satyasheel,Park, Eonjeong,Kim, Aejin,Lee, Sang Hwi,Kwak, Jong Hwan,Jung, Young Hoon,Kim, In Su
supporting information, p. 1654 - 1656 (2013/03/14)
A palladium-catalyzed decarboxylative acylation of phenylacetamides with α-oxocarboxylic acids via C-H bond activation is described. This protocol provides efficient access to a range of ortho-acyl phenylacetamides, which can be easily converted to 3-isochromanone derivatives. The Royal Society of Chemistry 2013.
Metaphenylenediamines in dyeing compositions for keratinic fibers
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, (2008/06/13)
Dye compositions comprising a coupler having to the formula STR1 in which formula R1 and R2 are identical or different and represent a hydrogen atom or an alkyl radical having 1 to 2 carbon atoms and n represents a number equal to 1 or 2 and a paraphenylenediamine. This coupler is particularly suitable for use in a dyeing composition comprising paraphenylenediamines responding to the formula STR2 or the corresponding acid salts; formula in which R1, R2 and R3 are identical or different and represent a hydrogen atom, an alkyl or alkoxy radical having 1 to 2 carbon atoms, R4 and R5 are identical or different and represent a hydrogen atom, a alkyl radical, hydroxyalkyl, alkoxyalkyl in which the alkoxy group comprises 1 to 2 carbon atoms, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoaminoalkyl, carbethoxyaminoalkyl, the alkyl groups in R4 and R5 having 1 to 3 carbon atoms, with the reservation that R1 or R3 represents hydrogen when R4 and R5 do not represent a hydrogen atom.
