During the development of new synthetic organic reactions by the use of group 47 metals, we twice encountered a reproducibility problem. The key factor was trace amounts of second metal elements that contaminated the first, main metals, i.e., nickel in chromium and lead in zinc. We had determined the standard procedures for these reactions and they were adopted in Organic Syntheses. The difference in the source of zinc, i.e., contamination by a catalytic amount of lead, proved to affect both the reactivity of the SimmonsSmith reaction and the formation of alkylzinc from the corresponding iodides. By using the concept of catalytic effects of the second metals, we developed a method to use manganese metal and applied this to sequential radical and anionic reactions. In addition, allylic aluminum species were prepared smoothly from allylic halides and aluminum by addition of an indium salt, the second element. In this account, I describe how the synthetic methods were discovered and developed, with an emphasis on the stories behind the communications and articles.
ASJC Scopus subject areas