6863-97-4Relevant academic research and scientific papers
Practical catalytic method for synthesis of sterically hindered anilines
Mailig, Melrose,Rucker, Richard P.,Lalic, Gojko
supporting information, p. 11048 - 11051 (2015/07/07)
A practical catalytic method for the synthesis of sterically hindered anilines is described. The amination of aryl and heteroaryl boronic esters is accomplished using a catalyst prepared in situ from commercially available and air-stable copper(i) triflat
Copper-catalyzed electrophilic amination of organozinc nucleophiles: Documentation of O-benzoyl hydroxylamines as broadly useful R2N(+) and RHN(+) synthons
Herman, Ashley M.,Johnson, Jeffrey S.
, p. 219 - 224 (2007/10/03)
This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents using O-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases, the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl-H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.
Benzyne Generation from Aryl Triflates
Wickham, Peter P.,Hazen, Kevin H.,Guo, Hong,Jones, Garth,Reuter, Kelly Hardee,Scott, William J.
, p. 2045 - 2050 (2007/10/02)
The use of aryl triflates to form arynes as reactive intermediates is decribed.This allows the first general use of phenols as aryne precursors.Phenyl triflate reacts with LDA at -78 deg C to form benzyne, which then reacts with diisopropylamine generating N,N-diisopropylaniline.Yields of diisopropylarylamines from aryne intermediates are superior to those previously reported.Regioisomeric ratios are similar to those obtained with use of other benzyne precursors.
