Aminomethylation catalysis

Jap-KIingermarm reactions, 4, 301 oxidation, 4, 299 reactions, 4, 299 synthesis, 4, 362 tautomerism, 4, 38, 200 Indole, 5-amino-synthesis, 4, 341 Indole, C-amino-oxidation, 4, 299 tautomerism, 4, 298 Indole, 3-(2-aminobutyl)-as antidepressant, 4, 371 Indole, (2-aminoethyl)-synthesis, 4, 278 Indole, 3-(2-aminoethyl)-synthesis, 4, 337 Indole, aminomethyl-reactions, 4, 71 Indole, 4-aminomethyl-synthesis, 4, 150 Indole, (aminovinyl)-synthesis, 4, 286 Indole, 1-aroyl-oxidation, 4, 57 oxidative dimerization catalysis by Pd(II) salts, 4, 252 Indole, 1-aroyloxy-rearrangement, 4, 244 Indole, 2-aryl-nitration, 4, 211 nitrosation, 4, 210 synthesis, 4, 324 Indole, 3-(arylazo)-rearrangement, 4, 301 Indole, 3-(arylthio)-synthesis, 4, 368 Indole, 3-azophenyl-nitration, 4, 49 Indole, 1-benzenesulfonyl-by lithiation, 4, 238 Indole, 1-benzoyl photosensitized reactions with methyl acrylate, 4, 268 Indole, 3-benzoyl-l,2-dimethyl-reactions... 

Zinc bromide catalysis effects a similar aminomethylation of silyl sulfides and phosphites (equation 11). ... 

New pyrazolyl ligands containing an aminomethyl group, in position 4, have been coordinated to rhodium(I) and show a good solubility in water, presumably because the ammonium group does not interact with the metal center. The resulting complexes have been characterized and, in our opinion, they are good candidates for biphasic catalysis [82], such as l,2,4-triazol-2-ium-5-ylidene complexes of Rh(I), Ir(I), Ni(0), Ni(II), Pd(II), and Hg(II) [83]. Due to their ionic character, these carbene complexes are extremely soluble in water. 

Pincer ligands, that is, tridentate Hgands that enforce meridional geometry upon complexation to transition metals, result in pincer complexes which possess a unique balance of stability versus reactivity [3]. Transition-metal complexes of bulky, electron-rich pincer ligands have found important appHcations in synthesis, bond activation, and catalysis [4, 5]. Among these, pincer complexes of Pr-PNP (2,6-bis-(di-iso-propylphosphinomethyl)pyridine), Bu-PNP (2,6-bis-(di-terPbutyl-phosphinomethyl)pyridine), and PNN ((2-(di-tert-butylphosphinomethyl)-6-diethyl-aminomethyl)pyridine), PNN-BPy (6-di-tert-butylphosphinomethyl-2,2 -bipyridine) ligands exhibit diverse reactivity [6-8]. These bulky, electron-rich pincer ligands can stabilize coordinatively unsaturated complexes and participate in unusual bond activation and catalytic processes. 

Further elaboration of 4 can be accomplished to install assorted functional groups of relevance for proton-transfer relays (Figure 3.5). For example, hydrolysis provides the dicarboxylic acid-appended terpy 5 [32], reduction with borane and hydrolysis yields the aminomethyl-terpy 6 [33], addition of azide provides the tetrazole-substituted terpy 7 [32], and treatment with hydrazine yields 8 [34]. Compounds 5-7 have been utilized as ligands for studying luminescence in lanthanide complexes [32, 33], but to our knowledge, have not yet been described in the catalysis literature. 

Toros S, Gemespecsi 1, Heil B, Maho S, Tuba Z. S3mthesis of new formyl and aminomethyl steroids via homogeneous catalysis. J. Chem. Soc., Chem. Commun. 1992 858-859. 

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