Manganese acetate, with alkenes

Manganese(III) acetate or chloride salts [Mn30(0Ac)7H0Ac, MnCh] can react with alkenes to afford... 

Manganese (III) acetate or chloride salts [Mn30(0Ac) H0Ac, MnCb] can react with alkenes to afford 1,2-dichlorides and chlorohydrin acetates (equation 16). i The manganese(III) reagent promotes the chlorination of 1,6-heptadiene (42) to afford almost equal amount of open chain and cycliz dichlorides... 

Manganic acetate (manganese triacetate), Mn(OCOCH3)3, is prepared by refluxing a solution of manganese acetate tetrahydrate in acetic acid with potassium permanganate [S03]. This oxidant hydroxylates ben-zylic methylene groups [416] and forms lactones from terminal alkenes [803, 804] (see equation 88). 

Other oxidative double bond azidations have been reported. Thus an azidohydrin was formed from pregnenolone acetate and chromyl azide (NaNs, Chromium(VI) Oxide) and steroidal dienones reacted with TMSNs/Leadf/V) Acetate to give diazido compounds. Vicinal diazides also result from alkenes and Fe Manganese(IH) Acetate (eq 9), or lodosylbenzene and NaNs. Anti-Markovnikov selenoazido products were prepared from the reaction of azide ion with alkenes and (Diace-toxyiodo)benzene/Diphenyl Diselenide (eq 10) a-keto azides (with TMSN3) are formed without PhSeSePh. ... 

The synthesis of functionalized 1,2-dioxane derivatives was developed using the tris(2,4-pentanedionato)manganese(lll)-alkene system and the man-ganese(III) acetate-1,3-dicarbonyl compoimd-alkene system. The endoper-oxidation catalytically proceeded in air imder very mild reaction conditions and the excellent yield of the endoperoxides was achieved, hi addition, heterocycle-fused or -substituted dioxanes could be synthesized according to the manganese(III)-catalyzed endoperoxidation. The hydroperoxidation also occurred in the reaction of the cyclic 1,3-diamides with alkenes. Furthermore, the direct hydroperoxidation of the cyclic 1,3-diamides was effective in the absence of alkenes. 

Earlier studies have also shown that a catalyst system consisting of palladium(II) and copper salts plus oxygen for the reoxidation did not work well,t in contrast to the result with the Wacker oxidation. However, if quinone or hydroquinone was added to a mixture of palladium acetate and copper acetate, oxygen could be used as an efficient oxidant for conversion of alkenes into allylic acetates. Thus, cyclohexene gave better than 85% cyclohexenyl acetate (Scheme 10). The combination of oxygen and cobalt or manganese acetate also works, but less well.t ... 

The reaction of //-phosphinates (712) with alkenes (713) in the presence of catalytic amounts of manganese(ii) acetate provided a simple and inexpensive way to prepare either symmetrically or differentially disub-stituted phosphinates (714) in moderate to good yields (Scheme 197). On the other hand, a direct heterocyclisation of (715) via intramolecular radical atylation, has been achieved using manganese(ii) acetate and excess of manganese(ii) oxide (Scheme 198). ... 

A hydroxy and an arylthio group can be added to a double bond by treatment with an aryl disulfide and lead tetraacetate in the presence of trifluoroacetic acid." Manganese and copper acetates have been used instead of Pb(OAc)4. ° Addition of the groups OH and RSO has been achieved by treatment of alkenes with O2 and a thiol (RSH)." Two RS groups were added, to give vie- dithiols, by treatment of the alkene with a disulfide RSSR and Bp3-etherate."° This reaction has been carried... 

A typical manganese-salen complex (27)[89] is capable of catalysing the asymmetric epoxidation of (Z)-alkenes (Scheme 18) using sodium hypochlorite (NaOCl) as the principle oxidant. Cyclic alkenes and a, (3-unsaturated esters are also excellent starting materials for example indene may be transformed into the corresponding epoxide (28) with good enantiomeric excess1901. The epoxidation of such alkenes can be improved by the addition of ammonium acetate to the catalyst system 911. 

Hwu et al. have examined the dependence of the metal oxidant on the mode of reactivity in silicon-controlled allylation of 1,3-dioxo compounds [95JOC856]. The use of manganese(III) acetate furnished the dihydrofuran product 22 only. On the other hand, use of cerium(IV) nitrate resulted in the formation of both acyclic (23) as well as the cyclized compound, with the product distribution dependent on the nature of the allylsilane. Facile synthesis of dihydrofurans by the cerium(IV) mediated oxidative addition of 1,3-dicarbonyl compounds to cyclic and acyclic alkenes has also been reported [95JCS(P1)187]. 

Polycyclic y-lactones. An intramolecular version of the formation of y-lactones by reaction of an alkene with acetic acid and manganese(HI) acetate (1) (6, 355-356) provides a general route to polycyclic y-lactones. Thus the unsaturated p-keto acid 2 cyclizes to the ds-bicyclic y-lactone 3 when warmed in acetic acid with 1 (1.3 equiv.)2... 

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