No abstract

The vinyl hydroperoxide (VHP), the major isomerization product of the syn-alkyl Criegee intermediate (CI) formed in alkene ozonolysis, is a direct precursor of hydroxyl radical (OH), the most important oxidant in the troposphere. While simulations of CI reactivity have usually assumed the VHP to be a prompt and quantitative source of OH, recent quantum chemical studies have revealed subtleties in VHP reactivity such as a barrier to peroxy bond homolysis and a possible rearrangement to a hydroxycarbonyl. In this work, we use M06-L, Weizmann-1 Brueckner Doubles, and equation-of-motion spin-flip coupled-cluster theories to calculate a comprehensive reaction mechanism for the syn and anti conformers of the parent VHP formed in trans-2-butene ozonolysis and the 1-methyl VHP formed in 2,3-dimethyl-2-butene ozonolysis. We predict that for the parent VHP the anti homolysis transition structure (TS) is 3 kcal mol lower in energy than the syn TS, but for the 1-methyl system, the syn TS is 2 kcal mol lower in energy. Statistical rate theory simulations based on the quantum chemical data predict that the parent VHP preferentially decomposes to vinoxy and OH radicals under all tropospheric conditions, while the 1-methyl VHP preferentially decomposes to 1-methylvinoxy and OH radicals only close to 298 K; at 200 K, the 1-methyl VHP preferentially rearranges to hydroxyacetone. Lower temperatures and higher pressures favor the temporary accumulation of both the parent and the 1-methyl VHP.

Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes with a limited array of substituents, are difficult to scale, or both. Herein, we disclose a new cyclopropane synthesis through the formal coupling of abundant carbon pronucleophiles and unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis of thianthrene in the presence of alkene substrates. We find that these dielectrophiles undergo cyclopropanation with methylene pronucleophiles via alkenyl thianthrenium intermediates. This protocol is scalable, proceeds with high diastereoselectivity, and tolerates diverse functional groups on both the alkene and pronucleophile coupling partners. To validate the utility of this new procedure, we prepared an array of substituted analogs of an established cyclopropane that is en route to multiple pharmaceuticals.

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Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes with a limited array of substituents, are difficult to scale, or both. Herein, we disclose a new cyclopropane synthesis through the formal coupling of abundant carbon pronucleophiles and unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis of thianthrene in the presence of alkene substrates. We find that these dielectrophiles undergo cyclopropanation with methylene pronucleophiles via alkenyl thianthrenium intermediates. This protocol is scalable, proceeds with high diastereoselectivity, and tolerates diverse functional groups on both the alkene and pronucleophile coupling partners. To validate the utility of this new procedure, we prepared an array of substituted analogs of an established cyclopropane that is en route to multiple pharmaceuticals.