%0 Journal Article %1 Bessenbacher.1989e %A Bessenbacher, Christian %A Kaim, Wolfgang. %D 1989 %J Journal of Organometallic Chemistry %K deazapteridine pteridine reductive silylation %N 1-2 %P 37--51 %T Stabilizing biochemically important intermediates through metal coordination. 5,8-Bis(trimethylsilyl)-5,8-dihydropteridine and its deaza derivative %V 362 %X Reductive trimethylsilylation of pteridine and its deaza derivs. 1,4,6- and 1,4,5-triazanaphthalene and quinoxaline yields the primary reduced forms of these heterocycles, which contain the 1,4-dihydro-1,4-diazine ring with 8 conjugated p-electrons as the only low mol. wt. products. Although the organometallic substituents stabilize these biochem. important yet normally short-lived dihydro forms and so allow unambiguous characterization by NMR, the non-cryst., colored compds. are still highly reactive. Unexpectedly, the deaza derivs. prove to be less electron-rich than the silylated dihydropteridine despite a clear increase in the electron d. in the arom. ring. The characteristic conformational flexibility of these intermediates is responsible for this inverse annulation effect. Reductive trimethylsilylation of 1,5-naphthyridine yields the 1-trimethylsilyl-1,4-dihydro deriv. as the major product. on SciFinder(R)

@article{Bessenbacher.1989e, abstract = {Reductive trimethylsilylation of pteridine and its deaza derivs. 1,4,6- and 1,4,5-triazanaphthalene and quinoxaline yields the primary reduced forms of these heterocycles, which contain the 1,4-dihydro-1,4-diazine ring with 8 conjugated \textgreek{p}-electrons as the only low mol. wt. products. Although the organometallic substituents stabilize these biochem. important yet normally short-lived dihydro forms and so allow unambiguous characterization by NMR, the non-cryst., colored compds. are still highly reactive. Unexpectedly, the deaza derivs. prove to be less electron-rich than the silylated dihydropteridine despite a clear increase in the electron d. in the arom. ring. The characteristic conformational flexibility of these intermediates is responsible for this inverse annulation effect. Reductive trimethylsilylation of 1,5-naphthyridine yields the 1-trimethylsilyl-1,4-dihydro deriv. as the major product. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Bessenbacher, Christian and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c7f76d187ea623ed9dc7e1f8de6f9922/huebleriac}, interhash = {ead6c81788da22e407b815aa2b40104c}, intrahash = {c7f76d187ea623ed9dc7e1f8de6f9922}, journal = {Journal of Organometallic Chemistry}, keywords = {deazapteridine pteridine reductive silylation}, number = {1-2}, pages = {37--51}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Stabilizing biochemically important intermediates through metal coordination. 5,8-Bis(trimethylsilyl)-5,8-dihydropteridine and its deaza derivative}, volume = 362, year = 1989 }