Synthesis of cyclohexadienylstannanes - Novel example of vinylic SRN1 mechanism: A theoretical and experimental study |
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| Authors: | Viviana B Dorn María T Lockhart Adriana B Pierini |
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| Institution: | a Departamento de Química, Universidad Nacional del Sur, Avenida Alem 1253, 8000 Bahía Blanca, Argentina
b INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba, Argentina |
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| Abstract: | The reaction of trimethyltinsodium (1) with 1-(diethoxyphosphoryl)oxy-1,3-cyclohexadienes in liquid ammonia under irradiation affords the corresponding 1-trimethylstannylcyclohexadienes. We suggest that these reactions occur by an SRN1 mechanism. On the other hand, 2-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene reacts very slowly towards 1 and the substitution product decomposes under the reaction conditions employed. Thus, structurally similar compounds do not behave in the same way under ET conditions. We suggest that this behavior is mainly due to differences in spin density of their radical anions, which affect their fragmentation rates. Our results are supported by computational calculations. |
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| Keywords: | Cyclohexadienyltin Vinylic SRN1 Trimethyltinsodium DFT |
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