Preparation of Alkyl Ethers with Diallyltriazinedione‐Type Alkylating Agents (ATTACKs‐R) Under Acid Catalysis

Abstract

Diallyltriazinedione‐type acid‐catalyzed alkylating agents (ATTACKs‐R) with 10 different alkyl groups (R), including benzyl, substituted benzyl, allyl, and methyl groups were synthesized. The palladium‐catalyzed intramolecular O‐to‐N allylic rearrangement of 2,4‐bis(allyloxy)‐6‐chloro‐1,3,5‐triazine was developed to introduce various alkoxy groups into the N,N′‐dialkylated triazinedione skeleton. O‐Alkylation of alcohols with ATTACKs‐R was carried out in 1,4‐dioxane in the presence of 2,6‐di‐tert‐butylpyridinium trifluoromethanesulfonate or trifluoromethanesulfonic acid as a catalyst. Six selected ATTACKs‐R bearing benzylic R groups were employed to prepare alkyl ethers from primary, secondary, and tertiary alcohols. The reactions of ATTACKs‐R bearing an o‐nitro‐substituted benzyl group tended to afford low yields. Comparison of four different triazinedione‐based benzylating reagents suggested that the N,N′‐substituents affected the reactivity.

Carbocationoids: a concept for controlling highly reactive cationic species

“…We previously reported the generation of benzylic carbocation species (e.g., benzyl trifluoromethanesulfonate) 18 from (benzyloxy)triazinediones through acid catalysis, using isocyanuric acids as the leaving group. [19][20][21] Based on these studies, we hypothesized that triazinedione compounds with suitable structures could serve as ligands for benzylic carbocations rather than their precursors. Thus, benzylic carbocationoids 3a and 3b (Scheme 1) were designed using triazinedione ligands 4a and 4b, respectively.…”