One-Step Synthesis of 2-Phosphonothiolanes by a New Pummerer-Phosphorylation Reaction: Stereoselective S-Oxidation

Abstract

A new one-pot Pummerer phosphorylation reaction allowed an efficient synthesis of 2-phosphonothiolanes starting from thiolane S-oxide and trialkyl phosphites. The S-oxidation of these cyclic sulfides occurred with a total trans-stereoselectivity.

Key words

Pummerer reaction - phosphorylation - phosphonothiolanes - sulfoxides - diastereoselectivity

References

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7

Various solvents (CH₂Cl₂, Et₂O, THF, CHCl₃) and reagents (TFAA or TMSOTf, Ac₂O, ClSiMe₃) were used from r. t. to -78 °C.

8

The modest yield obtained with (MeO)₃P is due to the sensitivity of the corresponding phosphonate ester in acidic medium (partial demethylation leading to phosphonic acid derivatives).

10

Compared to the previous work (see Ref. 4) no asymmetry was induced by the menthyl groups.

13

Atomic coordinates for 4e can be obtained on request from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 IEZ, UK. The crystal structure has been allocated the deposition number CCDC 142975.