N-tosyl derivatives

Dissolve in Et20, dry over KOH and distil. The N-Tosyl derivative has m 134-135° (from EtOH). [Chem Ber 96 550 1963.]... 

These workers also synthesized tryptamine stannane 161 and effected Stille couplings with this compound, including the intramolecular reaction 162 to 163 [171]. Eight- and 9-membered rings could also be fashioned in this manner. Other Pd catalysts were much less successful. The N-tosyl derivative of 162 was similarly prepared and used in Stille chemistry. 

Benzenium ions (199 X = acyl) on treatment with p-TSA in toluene undergo intramolecular O-alkylation to give the oxazolines (201 X=acyl Scheme 18, path b), rather than ring expansion to the lH-azepine as mentioned earlier for the N-tosyl derivative (Scheme 18, path a). However, these oxazolines are thermally labile and on heating at 180 °C rearrange in high yields (84-93%) to 1-acyl-1//-azepines (200 X = ArCO or Ac) <81AG(E)699>. 

The N-tosyl derivative 5, a possible precursor for the synthesis of ruthenium hydrogen transfer catalysts of type 6, is obtained in good yield by slow addition of TsCl in dichloromethane at 0 °C (eq 4). 

Decarbonylation. Sheehan and Frankenfeld treated a-imilino-a,a-diphenylacetic acid (1) with tosyl chloride in pyridine with the expectation of obtaining the N-tosyl derivative but instead characterized the products as benzophenone anil (3), carbon monoxide, and pyridinium tosylate. They postulate the intermediate formation of the mixed anhydride (2). 

Desulfonylation. Aziridines are released from their N-tosyl derivatives with sodium naphthalenide in THE... 

An air-filled stainless-steel autoclave containing N,N-dipropargylbenzamide, a little 10% Pd-on-carbon, KI, and methanol pressurized to 4 bar with CO, and stirred at 25° for 24 h 1-benzoyl-3,4-bis(methoxycarbonylmethylene)pyrrolidine (Y 95%), in acetonitrile containing NEtj stirred at 25° for 18 h under N2 dimethyl 1-benzoylpyr-role-3,4-diacetate (Y 68%). F.e. inch N-alkyl-, N-carbalkoxy-, and N-tosyl-derivs. s. G.P. Chiusoli et al.. Synthesis 1989, 262-5. 

Indoline allowed to react 2 hrs. at 0° with N-methyl-N-tosylpyrrolidinium per-dilorate in methylene chloride N-tosylindoline. Y 96.7%. - Similarly selective N-tosylation Startg. aminoalcohol -> N-tosyl deriv. Y 80%. F. e. s. T. Oishi et al., Chem. Commun. 1972, 1148. 

N-methyl amino acids are obtained by reaction of the N-tosyl derivative of the amino acid with methyl iodide, followed by removal of the tosyl substituent with HBr ... 

There are not too much examples of fluorinated pyrroles reactivity. Nevertheless one can easily conclude that fluoropyrroles have very similar chemistry in comparison to other pyrroles. Thus, fluorinated pyrrole 442 can be N-alkylated by treatment with alkyl bromides [18]. Inverse process is possible for N-tosyl derivative 445 under basic workup [84]. 

Nitrilases suitable for the transformations of alicyclic five- and six-membered y-amino nitriles were selected from the set of commercial nitrilases available from BioCatalytics Inc. (now Codexis) [59] and the effects of the substrate structure (ring size, protecting group, and trans versus cis configuration) were studied. N-tosylated derivatives of cis-3-amino cydopentane- and cyclohexanecarboxylic acids were obtained with the highest enantiopurities. Production of N-substituted pyrrolidine-and piperidinecarboxylic acids was also possible using the same nitrilases, but the enantiopurities of these products were generally low [60]. 

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