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DOI: 10.1055/a-1644-2806
Synthesis of Pentacoordinated Spiro[4.4]phosphoranes by Reaction of Cyclic Phosphazenyl Anions with Epoxides: Study of their P-Remote Functionalization and Hydrolysis
Financial support through Universidad de Almería (project PPUENTE2020/007) is gratefully acknowledged. P.M.S.P. thanks Fundación Alban for a doctoral fellowship.
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Abstract
The synthesis of a new family of pentacoordinated spiro[4.4]phosphoranes stabilized by the ortho-benzamide bidentate ligand (oBA, -C6H4-2-C(O)NH-) through reaction of Cα,C ortho -dilithiated phosphazenes with oxiranes is reported. Mixtures of epimers that differ in configuration at the phosphorus atom were obtained with moderate to high yields and diastereoselectivities. C3-Disubstituted derivatives could be separated, which provided access to enantiopure products arising from the reaction with (R)-2-phenyloxirane. Stereomutation was observed by heating the spirophosphoranes at 100 °C. Directed ortho-lithiation of spirophoshoranes followed by electrophilic quench reactions including carbon-based and heteroatom-based electrophiles afforded derivatives functionalized in a remote position with respect to the phosphorus atom. Benzoic acid catalyzed hydrolysis of spirophosphoranes furnished ortho-(γ-hydroxyalkylphosphoryl)benzamides by cleavage of the P–O and P–N bonds with retention of the phosphorus configuration. In contrast, alkaline hydrolysis led to the formation of γ-hydroxyphosphinic acids and benzamide.
Key words
spirophosphoranes - stereomutation - phosphazenes - phosphine oxides - hydroxyphosphinic acids - benzamides - hydrolysis - ortho-lithiationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1644-2806.
- Supporting Information
- CIF File
Publikationsverlauf
Eingereicht: 23. Juli 2021
Angenommen nach Revision: 14. September 2021
Accepted Manuscript online:
14. September 2021
Artikel online veröffentlicht:
27. Oktober 2021
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