Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

Abstract

Pyrimidyl alkanol and related compounds were found to be asymmetric autocatalysts in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde and related aldehydes. In the asymmetric autocatalysis with amplification of enantiomeric excess (ee), the very low ee (ca. 0.00005%) of 2-alkynyl-5-pyrimidyl alkanol was significantly amplified to >99.5% ee with an increase in the amount. By using asymmetric autocatalysis with amplification of ee, several origins of homochirality have been examined. Circularly polarized light, chiral quartz, and chiral crystals formed from achiral organic compounds such as glycine and carbon (13C/12C), nitrogen (15N/14N), oxygen (18O/16O), and hydrogen (D/H) chiral isotopomers were found to act as the origin of chirality in asymmetric autocatalysis. And the spontaneous absolute asymmetric synthesis was also realized without the intervention of any chiral factor.

Autocatalysis: Kinetics, Mechanisms and Design

“…Perhaps these strict mechanistic demands are the reason for the rarity of enantiomeric autocatalysis. With many excellent reviews available, [12h–j,l−n] we will only discuss its experimental examples briefly.…”

Chirogenesis and Pfeiffer Effect in Optically Inactive EuIII and TbIII Tris(β-diketonate) Upon Intermolecular Chirality Transfer From Poly- and Monosaccharide Alkyl Esters and α-Pinene: Emerging Circularly Polarized Luminescence (CPL) and Circular Dichroism (CD)

“…In recent years, controlled chirogenesis led by several scenarios of intermolecular chirality transfer endowed with natural and human-made resources has become the most popular phenomenon allowing for an efficient generation of the desired optically active substances in the realms of organic chemistry (Bosnich, 1967 ; Hayward and Totty, 1969 ; Noack, 1969 ; Soai et al, 2019 ), supramolecular chemistry (Kobayashi et al, 1993 ; Huang et al, 1998 ; Prince et al, 2000 ; Borovkov et al, 2004 ; Hembury et al, 2008 ; Aida et al, 2012 ; Borovkov, 2014 ; Liu et al, 2015 ; Goto et al, 2017 ), polymer chemistry (Green et al, 1993 ; Yashima et al, 1995 ; Nakashima et al, 2001 ; Kawagoe et al, 2010 ; Numata and Shinkai, 2011 ; Lee et al, 2012 ; Duan et al, 2014 ; Fujiki, 2014 ; Wang et al, 2014 ; Akagi, 2019 ), and molecular aggregation/colloidal/gel chemistry (Palmans and Meijer, 2007 ; Isare et al, 2010 ; George et al, 2011 ; Mei et al, 2015 ; Roose et al, 2016 ; Sang et al, 2019 ). Particularly, chirogenesis in metal coordination chemistry by the chirality transfer has long been one of the central subjects in inorganic chemistry 1 (Mason and Norman, 1965 ; Kirschner and Ahmad, 1968 ; Kirschner and Bakkar, 1982 ; Mason, 1982 ; Brittain, 1983 , 1989 ; Riehl and Richardson, 1986 ; Tsukube and Shinoda, 2002 ; Di Bari and Salvadori, 2005 ; Muller, 2009 , 2014 ; Bünzli, 2010 ; Carr et al, 2012 ; Tanner, 2013 ; Miyake, 2014 ; Kumar et al, 2015 ; Zinna and Di Bari, 2015 ; Kono et al, 2016 ; Longhi et al, 2016 ; Lunkley et al, 2018 ; Wong et al, 2019 ).…”

The Egg-Shaped Crystals That Should Not Be: A Brain-like Texture Combined with Single Crystallinity

“…The emergence of chirality in molecular materials, including crystals as observed in this study, from achiral precursors is a fascinating and complex phenomenon that is often related to origin of life studies. [28][29][30][31][32][33] Interestingly, we have found several isostructural and homochiral crystals having the same spacegroup (P622) but a wide range of morphologies and sizes. To this end, the coordination chemistry of metal-pyridine systems offers opportunities to generate fascinating mono-and multidomain, homogeneous single crystals.…”