Formation of enantioenriched alkanol with stochastic distribution of enantiomers in the absolute asymmetric synthesis under heterogeneous solid-vapor phase conditions.

Yoshiyasu Kaimori,Kenso Soai,Arimasa Matsumoto,Tsuneomi Kawasaki,Yui Hiyoshi

doi:10.1039/c9cc01875a

Abstract

Among several theories proposed for the origin of homochirality, absolute asymmetric synthesis is unique because it produces chiral compounds without the intervention of any chiral factor. Here we report on the kinetically controlled heterogeneous solid-vapor phase absolute asymmetric synthesis in conjunction with asymmetric autocatalysis with amplification of chirality. Each reaction, carried out in a test tube, between achiral powder crystals of pyrimidine-5-carbaldehyde and the vapor of diisopropylzinc, is controlled kinetically to afford either (S)- or (R)-pyrimidyl alkanol.

Highlights

Among several theories proposed for the origin of homochirality, absolute asymmetric synthesis is unique because it produces chiral compounds without the intervention of any chiral factor
Several theories have been proposed to explain the origins of the chirality of organic compounds, including circularly polarized light, chiral inorganic minerals, chiral crystals composed of achiral organic compounds, enantiotopic surfaces of achiral inorganic and organic crystals, chiral metal surfaces, spontaneous crystallization, and absolute asymmetric synthesis
Mislow proposed a new definition of absolute asymmetric synthesis as ‘‘asymmetric synthesis without the intervention of any chiral factor.’’1a It is widely accepted that organic reactions without the intervention of any chiral factor always give equal amounts of two enantiomers; i.e., racemate