5750-00-5Relevant articles and documents
Reagent-dictated site selectivity in intermolecular aliphatic C-H functionalizations using nitrogen-centered radicals
Carestia, Anthony M.,Ravelli, Davide,Alexanian, Erik J.
, p. 5360 - 5365 (2018/06/27)
The site selectivities of intermolecular, aliphatic C-H bond functionalizations are central to the value of these transformations. While the scope of these reactions continues to expand, the site selectivities remain largely dictated by the inherent reactivity of the substrate C-H bonds. Herein, we introduce reagent-dictated site selectivity to intermolecular aliphatic C-H functionalizations using nitrogen-centered amidyl radicals. Simple modifications of the amide lead to high levels of site selectivity in intermolecular C-H functionalizations across a range of simple and complex substrates. DFT calculations demonstrate that the steric demand of the reacting nitrogen-centered radical is heavily affected by the substitution pattern of the starting amide. Optimization of transition state structures consistently indicated higher reagent-dictated steric selectivities using more hindered amides, consistent with experimental results.
PREPARATION OF SOME ALKYL CHLORIDES BY DECOMPOSITION OF ALKOXYPHOSPHONIUM CHLORIDES AND BICHLORIDES
Denney, Donald B.,Garth, Bruce H.,Hanifin, J. William Jr.,Relles, Howars M.
, p. 275 - 280 (2007/10/02)
A number of alkoxyphosphonium chlorides and bichlorides have been prepared as stable intermediates or transient species.The thermal decompositions of these salts have been studied under a variety of conditions.The salts decompose by SN2 and SN1 processes in a fairly predictable manner.There are two decided advantages to using these salts as precursors to alkyl halides.The first is that in systems that are normally prone to rearrangements under substitution conditions, the products of decompositions of the salts are often formed with less rearrangement than is often found in other systems.The second is that the phosphates and phosphine oxides are excellent leaving groups and thus substitutions can be effected at centers that normally react very slowly.
