249563-60-8Relevant articles and documents
Stereochemistry of the Deamination of Spiropentylamine
Wiberg, Kenneth B.,Oesterle, Carmen
, p. 7763 - 7767 (2007/10/03)
The stereochemistry of the deamination of (-)-spiropentylamine in acetic acid has been studied, and it was found that one of the major products, (-)-spiropentyl acetate, was formed with essentially complete inversion of configuration. This suggests that it is formed via an SN2 displacement on the spiropentyldiazonium ion. The stereochemistry was established by the conversion of (-)-spiropentanecarboxylic acid to (-)-spiropentylamine via a Curtius rearrangement that proceeds with retention of configuration. The (-) acid also was converted to spiropentyl methyl ketone with methyllithium and then to (+)-spiropentyl acetate via the Baeyer-Villiger reaction that also results in retention of configuration. The deamination of N-nitroso-N-spiropentyl urea was studied in methanol, and spiropentyl methyl ether was a major product. Similarly, the reaction in water led to spiropentanol. The latter reactions also lead to 2-methoxymethyl- or 2-hydroxymethyl-1,3-butadiene, respectively, corresponding to the alternative mode of reaction via a cyclopropyl cation-allyl cation rearrangement.
