Olefins dihydroxylation

Certain tertiary amines such as pyridine or a-quinuclidine accelerate the stoichiometric reaction between osmium tetroxide and olefins (86). An asymmetric olefin osmylation using stoichiometric amounts of cinchona alkaloids as the chiral ligands was described in 1980 (87a). Optical yields of up to 90% were attained with fra/is-stilbene as substrate. 

Further efforts to design chiral ligands led to the highly enantioselective oxidation of rran.s-/3-methylstyrene (99% ee), rro/is-stilbene (97% ee), styrene (90%) mwty-3-heptene (90% ee), and dimethyl fumarate (93% ee) (87b f). Although this reaction is a reliable synthetic method, the metal s cost and toxicity necessitate its use as a catalyst. In 1988, Sharpless found that the desired enantioselective reaction can be achieved 

On the basis of X-ray and NMR studies of some cinchona alkaloid-0s04 complexes, Sharpless considers that the reaction occurs via pen- 

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More recently, a series of sol-gel hydrophobized nanostructured silica matrices doped with the organocatalyst TEMPO (SiliaCat TEMPO) entered the market as suitable oxidation catalysts for the rapid and selective production of carbonyls and carboxylic acids. In the former case, SiliaCat TEMPO selectively mediates the oxidation of delicate primary and secondary alcohol substrates into valued carbonyl derivatives (Scheme 5.2), retaining its potent activity throughout several reaction cycles (Table 5.2).33 Using this catalyst, for example, enables the synthesis of extremely valuable a-hydroxy acids with relevant selectivity enhancement by coupling of SiliaCat TEMPO with rapid Ru04-mediated olefin dihydroxylation (Scheme 5.3).34... 

DFT theory even seems to improve the performance of MP2 in cases where there is some small contribution of non dynamic correlation. This is seemingly the case in the BP86 computed first dissociation energies of a variety of metal carbonyls [51]. For instance, in the case of Cr(CO)6, the BP86 value is 192 kJ/mol, in exact (probably fortuitous) agreement with the (computationally most accurate) CCSD(T) value of 192 kJ/mol, but also reasonably close to the experimental value of 154 8 kJ/mol. In this case, the GGA DFT result improves clearly the local DFT SVWN value of 260 kJ/mol, and the MP2 result, wich is 243 kJ/mol. Comparable results can be found for the optimization of the Os-O distance in OsC>4 [52], which is relevant concerning olefin dihydroxylation. 

Abstract The reaction mechanism of the olefin dihydroxylation by transition metal... 

SCHEME 177. Coupled catalytic system for olefin dihydroxylation with H2O2 as terminal oxidant... 

The oxidation of sulfides to sulfones has been the subject of extensive studies, since sulfones are useful synthons for the construction of various chemically and biologically significant moleculesJ Recently, a new catalytic system has been developed by exchanging potassium osmate onto chloride-saturated layered double hydroxides (Figure 9.1), which we have shown to be an efficient catalyst for the direct oxidation of sulfides to sulfones, using molecular oxygen as the stoichiometric oxidant and with delivery of two oxygen atoms simultaneously to the sulfide, reminiscent of olefin dihydroxylation reactions. 

Organometallic compounds asymmetric catalysis, 11, 255 chiral auxiliaries, 266 enantioselectivity, 255 see also specific compounds Organozinc chemistry, 260 amino alcohols, 261, 355 chirality amplification, 273 efficiency origins, 273 ligand acceleration, 260 molecular structures, 276 reaction mechanism, 269 transition state models, 264 turnover-limiting step, 271 Orthohydroxylation, naphthol, 230 Osmium, olefin dihydroxylation, 150 Oxametallacycle intermediates, 150, 152 Oxazaborolidines, 134 Oxazoline, 356 Oxidation amines, 155 olefins, 137, 150 reduction, 5 sulfides, 155 Oxidative addition, 5 amine isomerization, 111 hydrogen molecule, 16 Oxidative dimerization, chiral phenols, 287 Oximes, borane reduction, 135 Oxindole alkylation, 338 Oxiranes, enantioselective synthesis, 137, 289, 326, 333, 349, 361 Oxonium polymerization, 332 Oxo process, 162 Oxovanadium complexes, 220 Oxygenation, C—H bonds, 149... 

BINAP, 127, 171, 191, 194, 196 olefin reaction, 126, 167, 169, 191 organic halides, 191 Pancreatic lipase inhibitors, 357 Pantoyl lactone, 56, 59 para-hydrogen, 53 Peptides, matrix structure, 350 Perhydrotriphenylene, crystal lattice, 347 Pericyclic reactions, 212 chiral metal complexes, 212 Claisen rearrangement, 222 Diels-Alder, 212, 291 ene reaction, 222, 291 olefin dihydroxylation, 150 Phase-transfer reactions asymmetric catalysis, 333... 

Included in this class of olefins is ( )-stilbene (entry 20), which throughout studies of AD has usually been the olefin dihydroxylated with the highest degree of enantioselectivity. Availability of (R,R) or (.5,5)-1,2-diphenyl-1,2-ethanediol (also referred to as stilbenediol or dihydrobenzoin) with high enantiomeric purities has led to reports of a number of applications, including incorporation into chiral dioxaphospholanes [50], chiral boronates [51], chiral ketene acetals [52], chiral crown ethers [53], and conversion into 1,2-diphenylethane-1,2-diamines [54]. Dihydroxylation of the substituted rran.r-stilbene 46 with Os04/NMO and DHQD-CLB gives the i ,/ -diol 47 with 82% ee in 88% yield [55]. 

In September 1997, Chemical and Engineering News summarized the ongoing discussion about the precise mechanism of the initial steps of the osmium-catalyzed olefin dihydroxylation in an... 

In a simplified catalytic cycle, reversible coordination of the dienophile to the Lewis acid (LA) activates the substrate toward diene cycloaddition. In the catalyst turnover event, the Lewis acid-product complex dissociate to reveal the de-complexed cycloadduct and regenerated catalyst (Scheme 2). While this catalytic cycle neglects issues of product inhibition and nonproductive catalyst binding for dienophiles having more than one Lewis basic site, the gross features of this process are less convoluted than many other enantioselective reactions e.g., olefin dihydroxylation, aldol reactions), a fact which may provide insight as to why this process is frequently used as a test reaction for new Lewis acid catalysts. 

The author proposed that the reaction presumably proceeded via [3+2] mechanism, which is quite similar to [3+2] mechanisms for olefin dihydroxylation. Insertion of OH into OsOa at pH = 12.1 led to the formation of 0s04(0H) species. Addition of C-H bonds into two oxo-groups of 0s04(0H) provided an intermediate, which can be hydrolyzed by aqueous base, and liberated a corresponding alcohol and reduced osmate [0s02(0H)4 ] (eq 80). 

Figure 7.10 Olefin dihydroxylation with 30% H2O2 over Nafion resin.

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