Enantioselective synthesis without discrete optically active additives.
By an adaptation of the asymmetric autocatalysis reactions of Soai, it was found that small enantiomeric excesses may be amplified to an arbitrary extent. When this process was applied 48 times to reactions in the absence of discrete optically active additives, all ultimately afforded substantial optical activity in the product. However, observations strongly suggest that most (and likely all) of these reactions are not true examples of absolute asymmetric synthesis. Rather, the ultimate optical activity arises from optically active impurities. Trace amounts of optically active materials may dominate the outcome of reactions involving asymmetric autocatalysis, and in the presence of opposite chiral influences a single enantiomer tends to take over a reaction. The possible implications of these observations to the origin of biological homochirality are noted.
Singleton
Daniel A
DA
Department of Chemistry, Texas A&M University, PO Box 30012, College Station 77842, USA. singleton@mail.chem.tamu.edu
Vo
Loan K
LK
D000447:Aldehydes / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods; D000432:Methanol / Q000737:chemistry; D011743:Pyrimidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D000447:Aldehydes; D011743:Pyrimidines; D015032:Zinc; D000432:Methanol