Unexpected metal-free transformation of gem-Dibromomethylenes to ketones under acetylation conditions.

@article{Kimura2015UnexpectedMT,
  title={Unexpected metal-free transformation of gem-Dibromomethylenes to ketones under acetylation conditions.},
  author={Rino Kimura and Yusuke Sawayama and Atsuo Nakazaki and Kazunori Miyamoto and Masanobu Uchiyama and Toshio Nishikawa},
  journal={Chemistry, an Asian journal},
  year={2015},
  volume={10 4},
  pages={
          1035-41
        }
}
Novel conditions for the transformation of gem-dibromomethylenes to ketones are described. gem-Dibromo compounds were treated with acetic anhydride and triethylamine in dichloromethane/water at room temperature under an air atmosphere to give the corresponding ketones in moderate yields. A radical mechanism is proposed based on experimental results. 
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A new synthetic strategy for the formation of the ABC tricyclic framework of saxitoxin was developed, which enables the concise stereocontrolled total synthesis of (+)-decarbamoyl-α-saxitoxinol, which is a naturally occurring saxit toxin analogue.

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