The past decade of organic chemistry may be charcterized as a period of violent development of new synthetic methods. This was accompained by a systematization of the analysis of synthetic problems (synthetic strategy). The planning of the synthesis of an organic target molecule is greatly facilitated by distinguishing between reagents X(C)n … with normal reactivity (acceptor properties at C1,3,5…, donor properties at X, C2,4…) and with reactivity umpolung (acceptor properties at X, C2,4…, donor properties at C1,3,5…). In this context, reactivity umpolung turned out to be useful as a heuristic principle, as a classification scheme, and as an aid for locating so-called strategic bonds (synthon, transform, and antithesis according to E. J. Corey). There are six principal methods of umpolung: 1 2n-oxidation, heteroatom exchange and modification, homologation and its reversal, the cyclopropane “trick”, use of acetylenes, and redox reactions; under certain circumstances none of these techniques is necessary in cases where direct umpolung is possible. Throughout the article, normal reactivity is indicated by green print; reactivity umpolung by red print.

Methods of Reactivity Umpolung

The synthetic utility of organohypervalent iodine reagents will be illustrated by their use in the α-hydroxydimethylacetal formation reaction from enolizable ketones, α-hydroxylation, α-tosyloxylation, α-alkoxylation and arylation of ketones, carbon−carbon bond formation, and intramolecular cyclopropanation using iodonium ylides. The uses of these reagents in the Hunsdiecker reaction of carboxylic acids and Hofmann rearrangement of carboxamides is presented. Specific transformation in the cubane series are discussed. The syntheses of a wide range of heterocycle structures are also presented. A unifying pathway for virtually all these diverse reactions is offered; the central features being initial attack at the iodonium center, ligand coupling, with reductive elimination of iodobenzene to yield the product.

Organohypervalent iodine: development, applications, and future directions.

Simulated large aspen tortrix (Choristoneura conflictana) herbivory of quaking aspen (Populus tremuloides) induces significant increases in concentrations of two phenol glycosides, salicortin and tremulacin, in leaves within 24 hr. Crushing of leaf tissue, as must occur when aspen leaves are eaten by chewing insects such as the large aspen tortrix, results in conversion of salicortin and tremulacin to 6-hydroxy-2-cyclohexenone (6-HCH). Salicortin, tremulacin, 6-HCH, and its degradation product, catechol, are all toxic to the large aspen tortrix when fed on an artificial diet. These damage-induced chemical changes provide a plausible mechanism for short-term resistance induced in aspen leaves by insect herbivory.

Chemical model for short-term induction in quaking aspen (Populus tremuloides) foliage against herbivores.

Direct α-hydroxylation of ketones under acidic conditions using [bis (trifluoroacetoxy)] iodobenzene

The synthetic uses of different peroxides for organic synthesis have been widely studied. Among these peroxides, meta-chloroperbenzoic acid (mCPBA) is an efficient oxidizing reagent and have been used for many oxidative transformations. mCPBA is widely used for chemical transformations such as the oxidation of carbonyl compounds, iminoindolines, olefins, imines, alkanes, silyl enol ethers, N- and S-heterocycles, active methylene groups, fluoromethylated allylic bromides, cyclic acetals, N-substituted phthalimidines, selenides, furans and phosphates. The purpose of this review is to collect and discuss the synthetic applications of meta-chloroperbenzoic acid (mCPBA) over the past few decades.

J. M. Gruber

Papers

m-Chloroperbenzoic acid oxidation of 2-trimethylsilyloxy-1,3-dienes. Synthesis of .alpha.-hydroxy and .alpha.-acetoxy enones