Oxymetallation. Part III. Competitive epoxidation during the hydridodemercuration of β-mercurated dialkyl peroxides with sodium borohydride

Cyclic peroxides by intramolecular peroxymercuration of unsaturated hydroperoxides

“…R, ^C-CHR., + HgY2 + HOO-f-Bu R" -RiRTXOO-f-Bu)-CH(HgY)R, 5 / .,\ R,R,C( OO-f-Bu R, R,R(00-i-Bu )-CKR; compounds can be efficiently converted into the corresponding /3-halogeno or /3-hydrido peroxides by halogeno-demercuration4 or hydridodemercuration. 5 We report here that intramolecular peroxymercuration is affected by reacting hydroperoxides such as 2 with mercuric(II) compounds. The versatile /3-mercurated cyclic peroxides so generated are a source of several new cyclic peroxide compounds.…”

Free radical reactions of organomercurials

“…97 In regard to the starting organomercurials, they can either lack functionality or be /3-substituted. 98,99 In subsections C of this section, the synthetic potential of radicals from the hydride reduction of organomercurials is discussed. The generation of radicals starting from organomercurials by means of metal hydrides, mainly sodium borohydride, together with their further use in the formation of carbon-carbon bonds by reaction with electron-poor alkenes has been called "the mercury method" (Scheme 25).11 This methodology has extensively been studied from a theoretical point of view.…”

Organomercury Compounds in Organic Synthesis

“…(44)] [83 -871. Equally valuable is the bromination Y X (44) l ' I PX x2 I I RCH=CHz --+ RCH-CHz --+ RCH-CHz Y = -OH, -OR'; X = B r , I of vinylmercury bromides which can apparently be controlled to give either the retained or inverted vinyl bromide simply by changing the solvent [eq. Several reports indicate that the halogenation of organomercurials prepared by solvomercuration reactions provides a convenient method for the synthesis of P-substituted organic halides [eq.…”

“…Several reports indicate that the halogenation of organomercurials prepared by solvomercuration reactions provides a convenient method for the synthesis of P-substituted organic halides [eq. (44)] [83 -871. Equally valuable is the bromination Y X (44) l ' I PX x2 I I RCH=CHz --+ RCH-CHz --+ RCH-CHz Y = -OH, -OR'; X = B r , I of vinylmercury bromides which can apparently be controlled to give either the retained or inverted vinyl bromide simply by changing the solvent [eq. (45)] [88].…”