Studies on Peroxy Compounds. VIII. The Preparation of Acylals and Related Compounds by Copper Salt Catalyzed Reaction of t-Butyl Perbenzoate with Simple Ethers and Sulfides.

An Efficient and Chemoselective Procedure for Acylal Synthesis

“…Beyond their protecting role, acylals are also important precursors for the synthesis of dienes, chiral allyclic esters and as cross linking reagents for the cellulose in cotton [ 2 , 3 , 4 , 5 ], hence methods for their synthesis have received considerable attention. Some of the reported catalysts for the preparation of 1,1-diacetates from aldehydes and acetic anhydride include Sc(OTf) 3 [ 6 ], PCl 3 [ 7 ], TMSCl (trimethylchlorosilane)-NaI [ 8 ], iodine [ 9 ], sulfuric acid [ 10 ], PVA-FeCl 3 [ 11 ], NBS ( N ‑bromosuccinimide) [ 12 ], triflic acid [ 13 ], Cu(OTf) 3 [ 14 ], CAN (ceric ammonium nitrate) [ 15 ], ZrCl 4 [ 16 ] and Bi(OTf) 3 [ 17 ]. Although some of these methods offer convenient protocols with good to high yields, the majority suffer from at least one of the following disadvantages: reactions under oxidizing conditions, use of halogenated solvents, high temperatures, long reaction times, moisture sensitivity of the catalyst, high cost and high toxicity.…”

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

“…The initial focus was on the most active catalyst, [Ni­(OAc) 2 ] in the model reaction of 1,4-dioxane ( 1a ) with cyclopropyl malonoyl peroxide ( P1 ) (Scheme ). In a number of studies α-acyloxy-ethers were synthesized with peroxides by using Cu or Fe-catalysis. ,− There is no reaction between 1,4-dioxane and peroxide P1 without a catalyst (Scheme ). The reactions with [Cu­(OAc) 2 ] and [Mn­(OAc) 2 ] led to acyloxylated ether 2a in 32% and 75% yields, respectively.…”