Periodinane, oxidation with

The Dess-Martin periodinane ( DMP ) reagent, U,l-tris(acetyloxy)-l,l-dihydro-l,2-benziodoxol-3(l//)-one, has also been used in several complex syntheses for the oxidation of primary or secondary alcohols to aldehydes or ketones, respectively (e.g., M. Nakatsuka, 1990). It is prepared from 2-iodobenzoic add by oxidation with bromic add and acetylation (D.a Dess, 1983). 

The second synthesis of crystalline 43 was reported by Mori as summarized in Scheme 62 [93]. The building block (4.R,5S)-A was prepared by an enzymatic process, while another building block C was synthesized via Sharpless asymmetric epoxidation. Coupling of A with C gave D, which was cyclized under Op-polzer s conditions to give crystalline E. When E was oxidized with Dess-Martin periodinane or tetra(n-propyl)ammonium perruthenate or Jones chromic acid, crystalline 43 was obtained. Swern oxidation or oxidation with 2,2,6,6-tetramethylpiperidin-1 -oxyl of E afforded only oily materials. Accordingly, oxidation of E to 43 must be executed extremely carefully. A synthesis of oily 43 was reported by Gil [94]. 

Martin, J. C. Arhart, R. J. J. Am. Chem. Soc. 1971, 93, 2339, 2341. J. C. Martin was a professor at the University of Illinois at Urbana, where he discovered the Martin s snl-furane dehydrating reagent. Martin also developed the Dess-Martin periodinane oxidation (page 195) with his student Daniele Dess. 

Molander and Hiersemann (60) reported the preparation of the spirocyclic keto aziridine intermediate 302 in an approach to the total synthesis of (zb)-cephalotax-ine (304) via an intramolecular 1,3-dipolar cycloaddition of an azide with an electron-deficient alkene (Scheme 9.60). The required azide 301 was prepared by coupling the vinyl iodide 299 and the aryl zinc chloride 300 using a Pd(0) catalyst in the presence of fni-2-furylphosphine. Intramolecular 1,3-dipolar cycloaddition of the azido enone 301 in boiling xylene afforded the desired keto aziridine 302 in 76% yield. Hydroxylation of 302 according to Davis s procedure followed by oxidation with Dess-Martin periodinane delivered the compound 303, which was converted to the target molecule (i)-cephalotaxine (304). 

Efficient new methods for oxidation are always welcome. The Dess-Martin periodinane has become the workhorse for alcohol to aldehyde or ketone conversion in organic research labs around the world. Viktor V. Zhdankin of the University of Minnesota, Duluth has described (Chem. Commun. 2004, 106) a complementary family of reagents. Oxidation of an ester I of o-iodobenzoic acid with NaOCl delivers 2. Depending on the ester, the reagent 2 is soluble and an effective oxidant, with KBr catalysis, in a wide range of organic solvents. Presumably, the spent oxidant can be recovered and recycled. 

Reactions of periodinane (40) with nucleophiles have been carried out. Treatment of (40) with two equivalents of f-butylamine gives 12-1-5 species (43) (or a stereoisomer) while the reaction with potassium hydroxide affords iodinane oxide (44) (or a bicyclic ring isomer). 

The o-iodosobenzoic or o-iodobenzoic acids, recovered from the work-up of oxidations with Dess-Martin periodinane, can be recycled back to this oxidant by oxidation to IBX, followed by transformation of IBX into Dess-Martin periodinane.2... 

It is possible to perform an oxidation with Dess-Martin periodinane under almost neutral conditions by adding pyridine to the reaction flask in order to neutralize the acetic acid, which is generated during the oxidation, and performing the work-up by treatment with sodium thiosulfate in the presence of a sodium bicarbonate buffer.2... 

Dess-Martin periodinane oxidizes the alcohol without affecting the primary aliphatic amine, which reacts in situ with the intermediate aldehyde, resulting in the formation of a new... 

The 2-(0-nitrobenzenesulfonamido)alcohol 359 was obtained from 358 through a sequence of reactions, which was then subjected to oxidation with Dess-Martin periodinane to give the 2-(t>-nitrobenzenesulfonamido)ketone 360 in 84% yield (Scheme 74). Upon reductive cyclization with hydrogen and palladium over activated carbon, 360 gave the 1,2,5-benzothiazepine 361 <2004T3349>. 

The periodinane (10) may also be prepared from o-iodobenzoic acid by oxidation with potassium bromate and then treatment with acetic anhydride18 (see Expt 6.36 for detailed formulation). It should be noted that the organic derivatives of pentacoordinate iodine(v) are termed periodinanes.18b This compound (the systematic name is l,l,l-triacetoxy-2,l-benzoxiodol-3(3//)-one) has found use as an oxidant of primary alcohols to aldehydes and alicyclic ketones to secondary alcohols it is claimed to have advantages over the chromium-based oxidation reagents. 

Scheme 21. Synthesis of orf/zo-imidoquinones and para-quinones by oxidation with Dess-Martin periodinane...

Martin periodinane to deliver the desired key intermediate, ketone 208. The total synthesis of 181 was finalized in two more steps (49% overall yield) by removal of the acetal and the MEM protective group with simultaneous formation of the desired intramolecular ketal 216, followed by cleavage of the Cl 1 TBDMS ether and in situ oxidation with IBX. The highly complex secondary metabolite 181 was thus accessed in 16 linear steps starting from 210 with an impressive 14% overall yield (Fig. 36). 

First an iodination of the alcohol is accomplished by treatment with iodine in presence of Ph3P and imidazole.13 Successive iodide displacement with the nucleophilic vinyl cuprate derived from 2-lithiopropene (2-bromopropene, tBuLi) finished the emplacement of the C-l side chain. Cleavage of the TPS ether by tetrabutylammonium fluoride and subsequent oxidation with the Dess-Martin periodinane provides aldehyde 9. 

The resulting carbacepham compounds have been stereospecifically substituted at C-7 with an ethyl or amino functionality to obtain compounds 162 and 163. Finally, carbacephem 164 can be obtained from carbacepham 163 by sequential oxidation with R.UO4 and Dess-Martin periodinane. 

Sugar oxazolines can be oxidized with m-CPBA and subsequently with Dess-Martin periodinane into nitroglycal derivatives<02TL347>. 

Corey and Roberts reported a total synthesis of the dysidiolide 46, a marine sponge metabolite with biological activities against A-549 human lung carcinoma and P388 murine leukemia cancer cell lines20 (Scheme 4.3p). The unwanted alcohol (47) was converted to the ketone 48 via Dess-Martin periodinane oxidation. The asymmetric reduction of 48 with the CBS catalyst 28b efficiently gave the alcohol 49, which was transformed into the dysidiolide 46 via photochemical oxidation. 

The aminocyclitol moiety was synthesized in a stereocontrolled manner from cis-2-butene-l,4-diol (Scheme 40)112 by conversion into epoxide 321 via Sharpless asymmetric epoxidation in 88% yield.111 Oxidation of 321 with IBX, followed by a Wittig reaction with methyl-triphenylphosphonium bromide and KHMDS, produced alkene 322. Dihydroxylation of the double bond of 322 with OSO4 gave the diol 323, which underwent protection of the primary hydroxyl group as the TBDMS ether to furnish 324. The secondary alcohol of 324 was oxidized with Dess-Martin periodinane to... 

---