Cerium ammonium nitrate secondary alcohols

Apart from sodium hypochlorite, a number of alternative secondary oxidants for TEMPO-mediated alcohol oxidations can be employed. These include cerium (IV) ammonium nitrate (CAN),24 trichloroisocyanuric acid (TCCA),25 oxone ,26 MCPBA,2,3,7 PhI(OAc)2,27 W-chlorosuccinimide,28 sodium bromite,29 electrooxidation,8,21 H5IO626 and a polymer-attached diacetoxybromide (I) complex.30... 

Cerium (TV) ammonium nitrate (CAN)37 and a cerium (TV) impregnated resin38 are able to catalyze the selective oxidation of secondary alcohols with sodium bromate (NaBrOi). Stoichiometric cerium bromate— CelBrCb h, prepared in situ from barium bromate and cerium (III) sulfate, is also able to perform selective oxidations of secondary alcohols.39... 

At the exotic end of the Lewis acid scale is tetrafluorosilane (mp -90 5C, bp -86 UC) first proposed by Corey and Yi as a mild and selective reagent for the cleavage of silyl-protected alcohols with the reactivity order being EtiSi > f-Bu-Me2Si f-BuPhiSi/ 1 The substrate in dichloromethane or acetonitrile, is stirred at room temperature under an atmosphere of excess tetrafluorosilane provided by a gas-filled balloon. The reaction is slow in dichloromethane but quite fast (ca. 15 min) in acetonitrile. In the final step of Yamamoto s synthesis of the Hemibrevetoxin B [Scheme 4.40]61 the secondary TIPS and TBS ethers were removed from 40.1 with tetrafluorosilane. Identical conditions were used by Nicolaou et al to remove two TBS ethers in the final step of their synthesis of Hemibrevetoxin B.62 In the example shown in Scheme 4,41, deprotection with fluoride (basic) or cerium(lV) ammonium nitrate (CAN) in methanol (neutral) isomerised the angelate to the more thermodynamically stable tiglate.63 However, with tetrafluorosilane, no isomerisation occurred during the deprotection step. 

Cyclic ethers are oxidized to lactones in the presence of cerium(IV) salts. Treatment of tetrahydiofu-ran with cerium(rV) ammonium nitrate in the presence of primary, secondary or tertiary alcdiols leads to the formation of the corresponding tetrahydrofuranyl ethers in quantitative yield. Fuitfaermoie, 4-meth-oxybenzyl ether derivatives of carbohytbates are selectively deprotected to the parent alcohols on reaction with cerium(IV) ammonium nitrate in aqueous acetonitrile. ... 

Ammonium cerium(IV) nitrate or cerium(IV) sulfate will catalyze the selective oxidation of secondaiy alcohols with sodium bromate as cooxidant, in this case remote C—C double bonds interfere, but 1,2-diols are not cleaved. It has been found that sodium bromite in aqueous acetic acid will act as a selective oxidant for secondary mary diols without the need for other catalysts (Scheme 21). ... 

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