Extreme Oxatriquinanes: Structural Characterization of alpha-Oxyoxonium Species with Extraordinarily Long Carbon-Oxygen Bonds


Gunbas G. , Sheppard W. L. , Fettinger J. C. , Olmstead M. M. , MASCAL M.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, cilt.135, ss.8173-8176, 2013 (SCI İndekslerine Giren Dergi) identifier identifier identifier

  • Cilt numarası: 135 Konu: 22
  • Basım Tarihi: 2013
  • Doi Numarası: 10.1021/ja4032715
  • Dergi Adı: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
  • Sayfa Sayıları: ss.8173-8176

Özet

The first stable alpha-oxyoxonium species have been synthesized and characterized. Strong donation of nonbonding electrons on oxygen into the adjacent sigma*(C-O+) orbital was predicted by modeling to result in unheard of carbon-oxygen bond lengths. The kinetic stability of the triquinane ring system provides a platform upon which to study these otherwise elusive species, which are evocative of intermediates on the acetalization reaction pathway. Crystallographic analysis of the alpha-hydroxy and alpha-methoxy oxatriquinane triflates reveals 1.658 and 1.619 angstrom C-O+ bond lengths, respectively, the former of which is a new record for the C-O bond.