Frequency of C-allylations on oligoglycinates via N-ylides
Hisao Nemoto1, Shin-ya Tamagawa, Kenji Yatsuzuka
1Department of Pharmaceutical Chemistry, Institute of Health Biosciences, Graduate School of The University of Tokushima, 1-78-1 Sho-machi, Tokushima 770-8505, Japan. nem@ph.tokushima-u.ac.jp
Abstract:
The highly selective mono-C-allylation of oligoglycinates such as a diethylenetriaminepentaacetate, an iminodiacetate, and an ethylenediaminetetraacetate via insertion of a vacuum operation between the N-allylation and C-migration steps is reported. It is contrastive that one-pot N-allylation-C-allylation procedure gave a mixture including multiallylated products. In the reaction with N-ylides, gem-C-diallylation and α,α'-C-diallylation of oligoglycinates are strongly inhibited even with the use of an excess of allyl bromide and base. A mechanism to explain this control of the frequency of C-allylation on oligoglycinates via N-ylides is also proposed.
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