Two types of intramolecular homolytic substitution reactions at group XIV atoms: unusual radical 1,4-Sn shifts from Si to C and carbonylative SHi reaction at Si
2003
Studer, Armido | Amrein, Stephan | Matsubara, Hiroshi | Schiesser, Carl H. | Doi, Takashi | Kawamura, Tomonori | Fukuyama, Takahide | Ryu, Ir-hyŏng
4-[(Trimethylstannyl)diphenylsilyl]butanoyl radical, arising from the corresponding 3-(stannylsilyl)propyl radical and CO, undergoes an SHi reaction at Si with extrusion of trimethyltin radical to give silacyclopentanone. The parent 3-(stannylsilyl)propyl radical was also found to isomerize to (3-stannylpropyl)silyl radical via a 1,4-Sn shift from Si to C with a rate constant of 9.3 × 10⁴ s⁻¹ at 80 °C. Ab initio and DFT MO calculations support a front-side attack mechanism.
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