Development of a New Benzylating Reagent Spontaneously Releasing Benzyl Cation Equivalents at Room Temperature

Abstract

A new O-benzylating reagent, that is, 4-(4,6-diphenoxy-1,3,5-triazin-2-yl)-4-benzylmorpholinium trifluoromethanesulfonate (DPT-BM), has been developed. Benzyl cation equivalents are generated from DPT-BM by dissolving the compound in a solvent at room temperature under non-acidic conditions. The benzylation of various alcohols by using a combination of DPT-BM and magnesium oxide provided the benzyl ethers in good yields.

Alcohol‐ and Amine‐Tolerant Synthesis of Six‐Membered Cyclic Quaternary Ammonium Salts by Using a Triazine‐Based Reagent

“…Initial experiments werec onducted with N,N-dibenzyl-N',N'-dimethyl-1,5-pentanediamine (2a), because it was predicted that reactionc onditions suitablef or the cyclization of the less nucleophilic dibenzylamino group [16,20,21] could be appliedt on umerous other startingm aterials. In polar methanol or acetonitrile, which are good solvents for the synthesis of the fivemembered pyrrolidiniumr ings 5, [16] the desired product 6a was only obtained in 36 and5 %y ield, respectively (Table1, entries 1a nd 2).…”

Development of Triazine-Based Benzylating Reagents Possessing <i>t</i>-Butyl Group on the Triazine Core: Thermally Controllable Reagents for the Initiation of Reaction

“…The copper-catalyzed crosscoupling of t-butyl magnesium chloride with cyanuric chloride afforded 2,4-di-t-butyl-6-chloro-1,3,5-triazine (3), 19) which was converted into 2,4-di-t-butyl-6-trifluoromethanesulfonyloxy-1,3,5-triazine (5) via 4,6-di-t-butyl-1,3,5-triazin-2(1H)-one (4) using our original method. 6,7,10,20) The treatment of 5 with N-benzylmorpholine in Et 2 O afforded 4-(4,6-di-t-butyl-1,3,5triazin-2-yl)-4-benzylmorpholinium triflate (X-b) as a precipitate in 89% yield.…”

“…1,2) Recently, we have developed several alkylating reagents based on the characteristics of 1,3,5-triazine. 2,4,6-Tris(benzyloxy)-1,3,5-triazine (TriBOT), 3,4) 2,4,6-tris(p-methoxybenzyloxy)-1,3,5-triazine (TriBOT-PM), 5) 6-(benzyloxy)-1,3,5-triazine-2,4(1H,3H)-dione (MonoBOT), 6,7) 2,4,6-tris(t-butoxy)-1,3,5-triazine (TriAT-tBu), 8) 2,4,6-tris(allyloxy)-1,3,5-triazine (TriAT-allyl), 9) and N,N′-dimethylated 6-(benzyloxy)-1,3,5-triazine-2,4(1H,3H)dione (DMBOT) 10) achieve the alkylation of various alcohols in good to excellent yields in the presence of a catalytic amount of an acid. 4-(4,6-Diphenoxy-1,3,5-triazin-2-yl)-4-benzylmorpholinium triflate (DPT-BM (X-a)) 11,12) converts acidor alkali-labile alcohols into corresponding benzyl ethers because of the nearly neutral conditions ( Fig.…”

N,N′‐Dimethylated Benzyloxytriazinedione: A Stable Solid Reagent for Acid‐Catalyzed O‐Benzylation

“…Although the Dudley reagent is stable enough to use in air, O ‐benzylation reactions with this reagent require high temperatures (83–120 °C) to proceed. Therefore, the development of a milder O ‐benzylation method using an easy‐to‐handle reagent is still desirable …”