Periodinane secondary alcohols

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). 

A vanety of secondary alcohols with terminal trifluoromethyl group are oxidized by the Dess-Martin periodinane reagent [52 57] (equation 48)... 

A vanety of secondary alcohols with terminal trifluoromethyl group are oxidized by the Dess-Martin periodinane reagent [52 53] (equation 48) Conversion of l,6-anhydro-4-0-benzyl-2 deoxy 2-fluoro-p-D-glucopyranose to the corresponding oxo derivative is earned out by ruthenium tetroxide generated in situ from ruthenium dioxide [54] (equation 49)... 

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. 

Like the Swem oxidation, the Dess-Martin periodinane (DMP) reagent oxidizes primary alcohols to aldehydes and secondary alcohols to ketones without using chromium or other heavy-metal compounds. The reaction with DMP takes place under mild conditions (room temperature, neutral pH) and gives excellent yields. The DMP reagent, which owes its oxidizing ability to a high-valence iodine atom, is a commercially available solid that is easily stored. 

The Dess-Martin periodinane reagent, used to oxidize primary alcohols to aldehydes and secondary alcohols to ketones. The DMP reagent uses a high-valence iodine atom as the oxidizing species, (p. 473)... 

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... 

Another reagent which undoubtedly will prove to be of real synthetic value is periodinane, which is an excellent, mild oxidant for primary (and secondary) alcohols. This reagent is discussed further in Section 2.9.3. 

Dess-Martin periodinane (mp 138-140 °C), which is derived from o-iodobenzoic acid, accomplishes the oxidation of primary and secondary alcohols under very mild conditions and in high yields [ 0, 801] (equation 18). 

The secondary alcohol is oxidized to the corresponding ketone with Dess-Martin periodinane in 99 % yield. 

The BH3-Me2S complex is a reagent to reduce carboxylic acids. Dess-Martin periodinane (33) is one of the standard reagents used to oxidize primary and secondary alcohols. 

Dess, D. B., Martin, J. C. A useful 12-1-5 triacetoxyperiodinane (the Dess-Martin periodinane) for the selective oxidation of primary or secondary alcohols and a variety of related 12-1-5 species. J, Am, Chem, Soc, 1991,113, 7277-7287. 

Full details for preparation of this tetravalent iodine compound arc now available.1 Since explosions have been reported in the preparation, the directions should be followed with care. Moreover, the reagent is sensitive to moisture, which converts it into iodosylbenzoic acid, also reported as explosive. The periodinane oxidizes primary and secondary alcohols rapidly and efficiently to carbonyl compounds without further oxidation to acids. Bcnzylic and allylic alcohols can be selectively oxidized. It does not react with sulfides or vinyl ethers. The iodine-containing by-product can be removed by hydrolysis to 2-iodosylbcnzoic acid. 

The Dess-Martin periodinane oxidation utilizes 1,1,1-triacetoxy-1,1 -dihydro-1,2-benziodoxol-3(lH)-one (2) as an oxidant for the conversion of primary and secondary alcohols (1) to their corresponding aldehyde (3) and ketone products, respectively. 

In modern organic synthesis Dess-Martin periodinane (DMP, structure 800 in Scheme 3.316) has emerged as the reagent of choice for the oxidation of primary and secondary alcohols to the respective carbonyl compounds. DMP is commercially available or can be conveniently prepared by the reaction of IBX with acetic anhydride (Section 2.2.3.2) [1211]. The synthetic applications of DMP have been summarized in several overviews [1102,1104,1212,1213]. 

Mild oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, employing the triacetoxyperiodinane (the Dess-Martin Periodinane reagent) ... 

Another more environmentally friendly class of oxidants than chromium species involve hypervalent iodine compounds, such as the reagent commonly referred to as the Dess-Martin periodinane (DMP). Hypervalent means a compound with a greater electron count than predicted by the octet rule. The name DMP derives from the two chemists that developed its reactivity, and its use is called the Dess-Martin oxidation. Once again, primary alcohols are oxidized to aldehydes, while secondary alcohols are oxidized to ketones, and tertiary alcohols are unreactive. Hence, DMP performs the same transformations as PCC and the Swern oxidation (same products as in Example 10.11). 

Secondary alcohols are oxidized to aldehydes using the Dess-Martin periodinane (DMP). 

Oxidation of a Secondary Alcohol to a Ketone (Sections 10.8A-10.8D) A secondary alcohol is oxidized to a ketone by chromic acid, by COjClj, DMSO, EtjN (Swem oxidation), or by DMP (Dess-Martin periodinane). 

For the most part, methods of ketone synthesis are similar to those for aldehydes. Secondary alcohols are oxidized by a variety of reagents to give ketones (Section 13.5). The choice of oxidant depends on such factors as reaction scale, cost, and acid or base sensitivity of the alcohol, with either the Dess-Martin periodinane or a Cr(VI) regent such as CrOa being a common choice. 

Dess-Martin periodinane (Section 17.7) An iodine-based reagent commonly used for the laboratory oxidation of a primary alcohol to an aldehyde or a secondary alcohol to a ketone. 

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