Cycloalkylation aniline

A selection of aromatic amines derived from tetrahydroisoquinolines is shown in Scheme 34. It is noteworthy that the products result only from sp -sp carbon-carbon bond formation at the benzyUc position of the substrates. The reaction was also carried out with dialkyl (or cycloalkyl) anilines as tertiary amines, and nitroethane and diethyl malonate as substrates [27]. 

The structure of the TS for the nucleophilic reaction of aniline at secondary cycloalkyl carbon centers depends on the size of the cycloalkyl group53. We note in Table 4 that although the rate is fastest with the cyclopentyl and slower with the cyclohexyl compound, the TS shifts successively to a later position along the reaction coordinate (more... 

TABLE 4. Rates and selectivity parameters for the nucleophilic reactions of anilines at cycloalkyl secondary carbon centers (c-(CF I2) lCHOSOiCfdLZ) in MeCN at 65.0 °C53... 

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