| P1843 | Phenoxydiphenylphosphine (1) |
5g 25g |
Thioetherification and azidation of tertiary alcohols by a new type of oxidation-reduction condensation using phenoxydiphenylphosphine (= phenyl diphenylphosphinite, 1) and azide compounds are reported by Mukaiyama and Kuroda’s group. These reactions proceed under mild and neutral conditions. Chiral secondary and the tertiary alcohols having an α-ester group are converted into the corresponding chiral sulfides and azides with inversion of the configuration.
When DEAD is employed as an oxidizing agent, condensation of tertiary alcohols and 2-nitrobenzoic acid affords the corresponding ester with inversion of the configuration.
These new types of oxidation - reduction condensations using 1 are applicable to sterically-hindered tertiary alcohols whereas the Mitsunobu reaction (PPh3-DEAD) is not.
References
a) K. Kuroda, Y. Maruyama, Y. Hayashi, T. Mukaiyama, Chem. Lett. 2008, 37, 836.[DOI] b) K. Kuroda, Y. Maruyama, Y. Hayashi, T. Mukaiyama, Bull. Chem. Soc. Jpn. 2009, 82, 381.[DOI] c) T. Mukaiyama, K. Kuroda, Y. Maruyama, Y. Hayashi, Chem. Lett. 2008, 37, 1072.[DOI] d) Review: T. Mukaiyama, K. Kuroda, Y. Maruyama, Heterocycles, 2010, 80, 63.[DOI]
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