Abstract
AbstractAsymmetric cyclopropanation of vinylphosphonates by using (S)‐dimethylsulfonium(p‐tolylsulfinyl)methylide and subsequent highly stereoselective methylation provided substituted cyclopropylphosphonates, which are useful intermediates in the synthesis of rigid aminophosphonic acids. However, in some examples desulfinylation by iPrMgCl led to 1,2‐migration of the phosphoryl group. The scope of this transformation was investigated by changing the temperature, electronegativity of the substituent α to phosphoryl group, and the configuration of the cyclopropylphosphonates. It was found that a cis relationship between the phosphoryl and sulfinyl groups led exclusively to the product of migration. It was proposed that the rearrangement occurred as an internal process in a concerted manner. The feasibility of an intramolecular mechanism was supported by DFT calculations. The products of desulfinylation with retained structure were used for the synthesis of enantiomerically pure 1‐aminocyclopropane‐1‐phosphonic acids.
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