Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

Beilstein Journal of Organic Chemistry

Vitali M. Boitsov¹  Alexander V. Stepakov²  Olesya V. Khoroshilova²  Alexander S. Filatov²  Anna G. Larina² 

[1] Saint-Petersburg National Research Academic University of the Russian Academy of Sciences, ul. Khlopina 8/3, 194021, St. Petersburg, Russian Federation;Saint-Petersburg State University, Universitetskaya nab. 7/9, 199034, St. Petersburg, Russian Federation;

关键词: azomethine ylides;    cycloaddition;    cyclopropenes;    dft calculations;    spiro heterocycles;   

DOI  :  10.3762/bjoc.18.77

来源: DOAJ

【 摘 要 】

A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexanes through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's purple (PRP) has been developed. Both 3-substituted and 3,3-disubstituted cyclopropenes reacted with PRP, affording the corresponding bis-spirocyclic 3-azabicyclo[3.1.0]hexane cycloadducts in moderate to good yields with high diastereofacial selectivity. Moreover, several unstable 1,2-disubstituted cyclopropenes were successfully trapped by the stable 1,3-dipole under mild conditions. The mechanism of the cycloaddition reactions of cyclopropenes with PRP has been thoroughly studied using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene–LUMOylide controlled while the transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the experimentally observed stereoselectivity.

【 授权许可】

Unknown