Synthesis and deamination of a deuterium-labeled spiropentylamine

Abstract

Spiropentylamine has been synthesized with a deuterium label in the 4 position. Nitrous acid deamination has yielded 2-and 3-methylenecyclobutanols with deuterium distributed such as to suggest a mechanism involving initial ring enlargement or bicyclobutonium ion formation. Comparison is made with hydrolysis of spiropentyl chloride, which gives 2-hydroxymethyl-1,3-butadiene as the major product. Previouswork in this laboratory1 has shown that the nitrous acid deamination of spiropentylamine (1) gives mainly the methylene cyclobutanols, 2 and 3. 1 HXO,.

The Chemistry of Highly Strained Oligospirocyclopropane Systems

“…By generating a cationic center in the α-position to a spiropentyl fragment upon solvolysis, a ring expansion was the predominant reaction pathway (Scheme ). 102b,, Spiropentyl cation, when generated by deamination of spiropentylamine ( 366 ), underwent a rearrangement with ring opening and ring expansion of both cyclopropanes (Scheme ). ,151a,,250a Opening of both rings, but with formation of 2-(hydroxymethyl)butadiene ( 370 ) as the main rearrangement product, was also observed upon solvolysis of the chloride 273 , tosylate 371 , and triflate 372 172a. All reactions have been investigated in great detail with regard to their mechanisms and the structures of the respective intermediates.…”

Synthesis and deamination of 4-aminospirohexane

“…Rearrangements of the spiropentyl cation 1 show a remarkable dual behavior, depending upon the mode of generation. 1 When spiropentylamine is deaminated with nitrous acid, the cation rearranges like a cyclopropylcarbinyl cation, giving methylenecyclobutanols 2. When chlorospiropentane ch2oh 3 is allowed to hydrolyze, the cation undergoes electrocyclic ring opening like a cyclopropyl cation, leading to 2-hydroxymethylbutadiene (3).…”

Spiropentyl cations formed by solvolysis reactions

“…This reaction presumably Study of the enzyme mechanism is considerably aided by mechanistic studies on analogous nonenzymic chemical reactions of appropriate model compounds. [1][2][3][4] In studies of this kind, one of the preferred factors for understanding the enzyme reactions is neighboring group participation in intramolecular reactions. Model compounds for adenosylmethionine should undergo nucleophilic attack at the sp3 carbon a to trivalent sulfur in aqueous media at moderate temperatures.…”