Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Transformation of Carbonyl Compounds into Homologous Alkynes under Neutral Conditions: Fragmentation of Tetrazoles Derived from Cyanophosphates

Transformation of Carbonyl Compounds into Homologous Alkynes under Neutral Conditions: Fragmentation of Tetrazoles Derived from Cyanophosphates
Masahiro Numata, Hiroki Yoneyama, Kenji Uemura, Shinya Harusawa, Yoshihide Usami
Cyanophosphates (CPs) can be easily prepared from either ketones or aldehydes, and their reaction with NaN3–Et3N·HCl results in the formation of azidotetrazoles. Under microwave irradiation, successive fragmentation of the azidotetrazoles generates alkylidene carbenes that undergo [1,2]-rearrangement and are transformed into homologous alkynes. Treatment of ketone-derived CPs with TMSN3 and Bu2SnO as catalyst in toluene at reflux directly yields the corresponding internal alkynes, whereas the reaction of aldehyde-derived CPs with NaN3–Et3N·HCl in THF at reflux or TMSN3–Bu2SnO (cat.) in toluene at reflux provides homologous terminal alkynes in good yields. These reactions take place under neutral conditions and can be successfully extended to obtain alkynes that are not usually accessible from the corresponding carbonyl compounds by the Ohira–Bestmann or Shioiri procedures, which require basic conditions.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00346

DOI: 10.1021/acs.joc.7b00346

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