The Scripps Research Institute

Hyconix, Inc.

University of Florida Research Foundation Inc

Periana, Roy a.

Konnick, Michael M.

Hashiguchi, Brian G.

Michael M Konnick

Brian G Hashiguchi

Roy A Periana

Steven M Bischof

Jeffrey T Elks

Juan Gamboa

Jeremy Patt

Johnathan Gorke

Provided is an oxidizing composition, in which a liquid medium is substantially inert in the presence of an oxidizing electrophile contained in the liquid medium. The composition comprises (a) an oxidizing electrophile comprising a main group element in oxidized form and at least one conjugate anion of an oxygen acid; (b) a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, and a combination thereof; and (c) optionally one or more salt additives. Further provided are a method of using the oxidizing composition to oxidize a substrate and a method of generating and/or regenerating an oxidizing electrophile comprising a main group element.

Oxidizing liquid media for chemical transformations

Provided is a method of producing an anhydride of an organic mono-acid comprising contacting an organic mono-acid and a thermally regenerable anhydride to produce the anhydride of the organic mono-acid, and either a diacid of the regenerable anhydride, a partially hydrolyzed regenerable anhydride, or both. In a particular example, acetic acid and glutaric anhydride can be reacted to form acetic anhydride.

Process for generating acid anhydrides

Provided is a process for converting an alkane to an alkene. The process comprises (a) contacting the alkane and either (i) an oxidizing electrophile comprising a main group element in oxidized form, or (ii) an oxidant and a reduced form of the oxidizing electrophile, in a liquid medium comprising an oxygen acid and optionally one or more additives selected from a non-oxidizable liquid, a salt additive, a Lewis acid, and water, to provide an oxidized intermediate and a reduced form of the oxidizing electrophile; (b) optionally separating the oxidized intermediate and the reduced form of the oxidizing electrophile; and (c) performing an elimination reaction on the oxidized intermediate to provide the alkene and the oxygen acid.

Oxidation of alkane to alkene

Provided is a process for oxidizing an alkene. The process comprises contacting an alkene, and either an oxidizing electrophile comprising a main group element in oxidized form or an oxidant and a reduced form of the oxidizing electrophile, in a liquid medium comprising an oxygen acid and optionally one or more additives selected from a non-oxidizable liquid, a salt additive, a Lewis acid, and water, to provide an oxygenate and a reduced form of the oxidizing electrophile. The process optionally further comprises separating the oxygenate and the reduced form of the oxidizing electrophile. The oxygenate can be further hydrolyzed to form an alcohol, diol, or polyol.

Direct oxidation of olefins to oxygenated species

The invention provides processes and materials for the efficient and cost-effective functionalization of alkanes, such as methane from natural gas, to provide esters, alcohols, and other compounds. The method can be used to produce liquid fuels such as methanol from a natural gas methane-containing feedstock. The soft oxidizing electrophile, a compound of a main group, post-transitional element such as Tl, Pb, Bi, and I, that reacts to activate the alkane C&#x2014;H bond can be regenerated using inexpensive regenerants such as hydrogen peroxide, oxygen, halogens, nitric acid, etc. Main group compounds useful for carrying out this reaction includes haloacetate salts of metals having a pair of available oxidation states, such as Tl, Pb, Bi, and I. The inventors herein believe that a unifying feature of many of the MXn electrophiles useful in carrying out this reaction, such as Tl, Pb, and Bi species, is their isoelectronic configuration in the alkane-reactive oxidation state; the electrons having the configuration [Xe]4f145d10, with an empty 6s orbital. However, the iodine reagents have a different electronic configuration.

Oxidation of alkanes to alcohols

Provided are methods and materials for the functionalization of a heteroalkane or arene using an oxidizing electrophile as a stoichiometric agent or catalyst. The reaction involves the replacement of a hydrogen atom on an sp3-hybridized carbon atom of the heteroalkane or of a hydrogen atom on an sp2-hybridized carbon atom of the arene. A main group element organometallic intermediate is formed that undergoes further conversion to a functionalized heteroalkane or arene.

Process for the functionalization of heteroalkanes and arenes

The invention provides processes and materials for the efficient and costeffective functionalization of alkanes and heteroalkanes, comprising contacting the alkane or heteroalkane and a soft oxidizing electrophile comprising Se(VI) or Te(VI), in an acidic medium, optionally further comprising an aprotic medium, which can be carried out at a temperature of less than 300 C. Isolation of the alkylselenium or alkyltellurium intermediate allows the subsequent conversion to products not necessarily compatible with the initial reaction conditions, such as amines, stannanes, organosulfur compounds, acyls, halocarbons, and olefins.

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Aurora, IL, United States of America

Michael M Konnick