Oxidation

Chaloner, Penny A.

doi:10.1016/b978-0-408-10776-1.50010-0

Cited by 11 publications

(9 citation statements)

References 513 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Those substrates that react to form N−C, S−C, and O−C single bonds (i.e., amines, thiols, and alcohols) can be thought of doing so by nucleophilic attack at the new Re−C bond. It is well known that atoms become more electrophilic upon coordination to a high oxidation-state metal. ,, Indeed, were there neither these nor other examples, the conversion of the normally nucleophilic peroxide ion into an electrophilic center upon coordination to MTO would provide a convincing illustration. The nucleophilic center (the heteroatom) of RNH 2 , RSH, and ROH will attack the carbon atom of A C .…”

Section: Discussionmentioning

confidence: 99%

Organic Reactions Catalyzed by Methylrhenium Trioxide: Reactions of Ethyl Diazoacetate and Organic Azides

1996

View full text Add to dashboard Cite

Methylrhenium trioxide (CH 3 ReO 3 or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, R-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of R-phenoxy ethyl acetates. The use of EDA to form R-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed.In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and to benzil; at the same time the epoxide was converted to an olefin. These results provide further support for the proposed intermediate, a cyclic species containing Re, O, and CHCO 2 Et (or, occasionally, CPhC(O)Ph) in a three-membered ring.

show abstract

Section: Discussionmentioning

confidence: 99%

Organic Reactions Catalyzed by Methylrhenium Trioxide: Reactions of Ethyl Diazoacetate and Organic Azides

1996

View full text Add to dashboard Cite

show abstract

“…Oxidative addition of a carbon−heteroatom bond to a transition metal complex constitutes the key catalytic step involved in a number of transition metal-catalyzed transformations . Particularly successful examples in view of organic synthesis are those that involve carbon−halogen bonds.…”

mentioning

confidence: 99%

The First Example of Facile Oxidative Addition of Carbon−Tellurium Bonds to Zero-Valent Pt, Pd, and Ni Complexes

1997

View full text Add to dashboard Cite

“…With the dyes 3 and 4 in hand, we were able to implement the rapid screening protocol. Twelve hydrosilation catalysts 9a-c were assayed (Table ). Some were known to be active (e.g., entries 4 and 6), some were not previously studied for alkene hydrosilation (entries 8 and 10 9d ), and one was an entirely new compound (entry 11).…”

mentioning

confidence: 99%

“…Assays were run in a homemade 60-well plate machined from 3 / 4 -in Teflon (well capacity, 1 mL) in a glovebox under N 2 and Ar . Stock solutions of Ph 2 SiH 2 (5.0 × 10 -2 M),9e dye (alkene, 3.3 × 10 -4 M; imine, 6.6 × 10 -4 M),9f and catalysts (3.3 × 10 -4 M) were prepared in degassed anhydrous THF. Fixed volumes (silane, 0.100 mL; dye, catalyst 0.200 mL each) of the stock solutions, added to the appropriate wells with an adjustable microliter pipet, delivered the following molar amounts to each well: catalyst, 66 nmol; alkene dye, 66 nmol; imine dye, 130 nmol; silane, 5.0 μmol.…”

mentioning

confidence: 99%