Reaction of iodonium nitrate with some olefinic alcohols

Abstract

lodonium nitrate in pyridine-chloroform at room temperature undergoes preferential electrophilic addition to certain olefinic alcohols to form (i) hydroxyiodoalkyl nitrates and (ii) hydroxyiodoalkylpyridinium nitrates. Parallel reactions in sym-collidine-chloroform gave three-, four-, and five-membered cyclic ethers as well as products of type

Kinetics and energetics of the addition of iodonium nitrate to unsaturated systems

“…Assuming both the iodonitrate ester and the iodopyridinium salt are formed from the same intermediate iodonium ion, structure 2 is proposed for the salt. Parallel reaction of iodonium nitrate in chloroform-sym-collidine with cyclohex-2-en-1-01 gave 1 in 55% yield (3). The stereochemistry of the two possible products favors an intermediate of type 3 and proves that the iodonium ion is formed cis to the hydroxyl group.…”

“…The effect of this complexation ticularly in electrophilic additions to a wide range may alter its relative electrophilicity compared to of unsaturated substrates (1)(2)(3)(4). Hodonium nitrate other iodine containing pseudohalogens such as (generated by the reaction of iodine chloride iodine isocyanate, iodine chloride, and iodine with silver nitrate in chloroform-pyridine) like azide depending on the electronic and steric lidine added-to suitable olefinic substrates gives other pseudohalogens has all the characteristics cyclized and,or addition products depending of an electrophilic reagent which is consistent upon the structure of the substrate (2,3). These with the qualitative observation that electron-results were in contrast to the known chemistry donating groups facilitate the reaction while of iodine isocyanate (5) and iodine azide (6).…”

Influence de la complexation sur la réactivité de nitrates d'halogènes

“…Le nitrate d'iode, obtenu <<in situ>> par riaction de l'iode sur le nitrate d'argent en milieu organique, peut Ctre complex6 par deux molCcules de pyridine et, ainsi isolC, conservC 2 1 l'abri de l'air. La rCactivitC de ce complexe sur les composCs CthylCniques a CtC Ctudite par Diner et al (2)(3)(4). La rkaction d'addition fournit les nitrates d'iodoalkyles attendus, accompagnCs de nitrates d'iodoalcanes pyridinium.…”

Addition of pseudohalogens to unsaturated carbohydrates. VI. Synthesis of 4′ -thiocordycepin

“…The addition of iodine nitrate to a furanoid derivative having an exocyclic double bond has already been reported (3); also, reactions with steroidal (4) and other noncarbohydrate olefins (5) have been studied. The pseudohalogen has been prepared by a variety of methods.…”