A Practical Method for p-Methoxybenzylation of Hydroxy Groups Using 2,4,6-Tris(p-methoxybenzyloxy)-1,3,5-triazine (TriBOT-PM)

Abstract

A new acid-catalyzed p-methoxybenzylating reagent, 2,4,6-tris(p-methoxybenzyloxy)-1,3,5-triazine (TriBOT-PM), has been developed. The reaction of acid-and alkali-labile alcohols with TriBOT-PM in the presence of a catalytic amount of various acids (TfOH, BF 3 ·OEt 2 , CSA, etc.) afforded the corresponding pmethoxybenzyl ethers in good yields. Since TriBOT-PM is an airstable crystalline solid and can be prepared from inexpensive materials, i.e. cyanuric chloride and anisyl alcohol, this route is of practical use.

Development of a Purely Isolable (Dimorpholino)triazine-Based Reagent for the Epoxidation of Alkenes

“…The formation of a thermodynamically stable triazinone scaffold is a key driving force for epoxidation. Such triazinone-leaving groups have also been used in several triazine-based reagents developed for dehydrative condensation [2][3][4][5][6] and acid-catalyzed alkylation [7][8][9][10][11][12][13] . Triazox can be isolated as a bench-stable solid, in contrast to traditional organic oxidants for epoxidation reactions, such as mCPBA (typically used as a hydrate with ~80% purity) [14][15][16] and DMDO (prepared immediately before use) [17][18][19] .…”

Total Synthesis of (−)-Enigmazole B

“…The synthesis of terminal alkyne 11 commenced with known alcohol 22 (dr > 95:5, er 95:5), 22 as depicted in Scheme 2B. Protection of 22 at its para-methoxybenzyl (PMB) ether 23 and desilylation delivered alcohol 23 (77%, two steps). Dess− Martin oxidation of 23, followed by Horner−Wadsworth− Emmons reaction with phosphonate 14, gave α,β-unsaturated imide 24 (85%, two steps).…”

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

“…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.…”