Aprile Antonino, Iversen Kalon J, Wilson David J D, Dutton Jason L
Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, Victoria, Australia, 3086.
Inorg Chem. 2015 May 18;54(10):4934-9. doi: 10.1021/acs.inorgchem.5b00537. Epub 2015 Apr 30.
We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant PhI(4-DMAP)2. Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.
我们报道了一种通过使用I(III)氧化剂PhI(4-DMAP)2将Te(II)中心氧化为Te(IV)，在1,2-二苯基碲吩的3-位发生的新型C-H到C-N键复分解反应。瞬态Te(IV)配位化合物自发还原为Te(II)会生成4-DMAP的亲电等价物，该等价物会在碲吩的3-位的C-H键处发生取代反应。理论和合成反应途径研究证实，与4-DMAP形成的Te(IV)配位络合物是中间体。在这些途径研究过程中，还发现由PhI(OAc)2和2 TMS-OTf生成的I(III)氧化剂的身份是PhI(OAc)(OTf)，而不是先前认为的PhI(OTf)2。
