Selective Formation of Allylic Hydroperoxides<scp>via</scp>Singlet Oxygen<scp>ene</scp>Reaction

Orfanopoulos, Michael; Vougioukalakis, Georgios C.; Stratakis, Manolis

doi:10.1002/9780470682531.pat0355

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“…Sulfur monoxide prefers to undergo cheletropic [2 + 1]-addition with alkenes giving the corresponding thiirane 1-oxides for which no rearrangement into the corresponding product of ene-reaction has been reported yet. This is surprising when comparing with the ene-reaction of singlet oxygen − and related ene-reactions of diazene derivatives − and nitroso compounds. − Exothermicities of ca. −13.4 and −15.6 kcal/mol are estimated for the ene-reactions of triplet dioxygen (based on Δ H f ° (MeOOH) = −31.3 kcal/mol, Δ H f ° (CH 4 ) = −17.9 kcal/mol) and diazene (based on Δ H f ° (HNNH) = 50.9 kcal/mol; Δ H f ° (propane) = −25.0 kcal/mol, Δ H f ° (CH 3 CH 2 CH 2 NHNH 2 ) = +11.4 kcal/mol).…”

Section: Introductionmentioning

confidence: 99%

Desulfinylation of Prop-2-enesulfinic Acid: Experimental Results and Mechanistic Theoretical Analysis

et al. 2009

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The potential energy surfaces of the desulfinylation of prop-2-enesulfinic acid (13) in CH(2)Cl(2) solution at -15 degrees C have been explored by quantum calculations and analyzed with kinetic data obtained for the reaction in absence or presence of additives. Monomeric 13 adopts a preferred conformation with gauche S=O/sigma(C(1)-C(2) bond pairs and the O-H bond pointing toward C(3). It equilibrates with the more stable dimer (13)(2) (at -15 degrees C) formed by two O-H...O=S hydrogen bonds and in which the S=O/sigmaC(1)-C(2) are gauche also, but the SOH moieties are antiperiplanar with respect to sigma(C(1)-C(2)). Dimer (13)(2) undergoes desulfinylation into propene + SO(2) + 13 following a one-step, concerted mechanism. The preferred transition state is a six-membered, chairlike transition structure (C...S elongation and S-O...H...C(3) hydrogen transfer occur in concert) in which the S=O/sigma(C(1)-C(2)) bonds are gauche (S=O adopt pseudoaxial positions). There are at least 48 transition states, each one defining a different pathway, all with similar calculated free energies (DeltaG(double dagger) = 25.3-28.6 kcal/mol), which makes the bimolecular (autocatalyzed) retro-ene elimination of SO(2) competing (entropy factor) with a monomolecular process for which the transition state (calculated DeltaG(double dagger) = 24.3 kcal/mol) implies only one molecule of sulfinic acid. This agrees with the experimental rate law of the reaction which is first order in the concentration of dimer (13)(2). SO(2), CF(3)COOH, and BF(3) x Me(2)O do not catalyze the reaction. In the presence of an excess of BF(3) x Me(2)O the desulfinylation is completely inhibited due to the formation of a stable tetramolecular complex of type (CH(2)=CHCH(2)SO(2)H x BF(3))(2) (18), for which quantum calculations show that the S=O/sigma(C(1)-C(2)) bonds are antiperiplanar whereas the S-OH/sigma(C(1)-C(2)) bonds are gauche. Independently of the additive, the retro-ene eliminations of SO(2) are calculated to be concerted and have transition states adopting six-membered cyclic structures in which S=O and sigma(C(1)-C(2)) are gauche, the S=O interacting with the additive. Preliminary experiments suggested that the thermodynamically unfavored ene reaction of SO(2) with propene can occur at low temperature using 1 equiv of BF(3).

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