Regio- and Stereo-Controlled Alkoxyiodination of 1,3-Diene Using Iodine-Cerium(IV) Ammonium Nitrate

Abstract

Reaction of 1,3-cycloalkadienes (cyclopentadiene, cyclohexadiene, and cycloheptadiene) with iodine-cerium(IV) ammonium nitrate in alcohols, gave the corresponding regiospecific trans-2-alkoxy-1-iodo compounds as major products accompanied with 1,4-dialkoxy compounds as by-products. In the case of CH3CN-H2O as solvent, trans-iodohydrins were obtained. Thus the reaction of cyclic and acyclic 1,3-diene derivatives using this synthetic method afforded the 1,2-addition alkoxyiodo compounds preferentially.

Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant

“…Under the same reaction conditions, isophorone (3,5,5-trimethyl cyclohex-2-ene-1-one) was found to undergo oxidative rearrangement with 1,2-migration of the C 5 -methyl group. Cycloalkenes on treatment with iodine and CAN in alcohols such as methanol, ethanol, 1-propanol, or 2-propanol under reflux conditions gave the corresponding vicinal alkoxyiodo cycloalkanes. , When the solvent was tert -butyl alcohol, the product was trans -iodonitrate .…”

Electrophilic Iodination of Organic Compounds Using Elemental Iodine or Iodides

“…95 Reactions of cyclic and acyclic 1,3-diene derivatives with iodine and ammonium cerium(IV) nitrate (CAN) in alcohols or acetonitrile-water gave the corresponding regiospecific trans-2-hydroxy-or trans-2-alkoxy-1-iodo compounds as major products, accompanied by 1,4-dialkoxy derivatives as by-products. 96 This reaction, improved by further treatment of primarily formed trans-iodonitrate or trans-iodoacetate with aqueous potassium hydroxide, was used as a new selective and efficient method for preparation of cis-diols. 97 Organotelluride compounds were used as water soluble catalysts for the regio and stereo selective oxidative iodination of alkenes with the sodium iodide and hydrogen peroxide system.…”

Carbon-Heteroatom Bond-Forming Reactions Mediated by Cerium(IV) Ammonium Nitrate:An Overview

“…64 Cyclic1,3-dienes afford the corresponding trans-2-alkoxy-1-iodo compounds as the major products on treatment with iodine and CAN in alcohols (Scheme 31). 65 The reaction is generally applicable to the synthesis of a variety of 1,2-trans alkoxyiodides. …”

“…64 Cyclic1,3-dienes afford the corresponding trans-2alkoxy-1-iodo compounds as the major products on treatment with iodine and CAN in alcohols (Scheme 31). 65 The reaction is generally applicable to the synthesis of a variety of 1,2-trans alkoxyiodides. i 35a R 1 = R 2 = H, R 3 = Me (66%) 35b R 1 = R 2 = R 3 = H (67%) 35c R 1 = R 2 = H, R 3 = Cl (52%) 35d R 1 = Cl, R 2 = R 3 = H (46%) 36a R 1 = R 2 = H, R 3 = Me (70%) 36b R 1 = R 2 = R 3 = H (71%) 36c R 1 = R 2 = H, R 3 = Cl (68%) 36d R 1 = Cl, R 2 = R 3 = H (54%)…”