3395-83-3Relevant articles and documents
Electrochemical Obtention of cis- and trans-3,6-Dimethoxy-3,6-dimethyl-1,4-cyclohexadienes
Barba, Fructuoso,Guirado, Antonio,Barba, Isidoro
, p. 3022 - 3024 (1984)
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Thiol-initiated photocatalytic oxidative cleavage of the C=C bond in olefins and its extension to direct production of acetals from olefins
Wang, Xinglin,Li, Yuanyuan,Li, Zhaohui
, p. 1000 - 1006 (2021/02/26)
The oxidative cleavage of olefins to produce aldehydes/ketones is an important reaction in organic syntheses. In this manuscript, a mild and operationally simple protocol for the aerobic oxidation of olefins to produce carbonyl compounds was realized over ZnIn2S4under visible light, using air as the oxidant and a thiol as the initiator. It was proposed that the photogenerated holes over ZnIn2S4attack the thiol to produce thiyl radicals, which initiate the oxidative cleavage of the C=C bond in olefins to produce aldehydes/ketones. By further coupling with the condensation between the as-obtained aldehydes/ketones and alcohols, this strategy can also be applied to the production of different acetals directly from the olefins. This study demonstrates a new pathway to realize the oxidative cleavage of olefins to produce aldehydes/ketones, and also provides a new protocol for the production of acetals directly from the olefins.
Enantioselective, Catalytic Multicomponent Synthesis of Homoallylic Amines Enabled by Hydrogen-Bonding and Dispersive Interactions
Ronchi, Elisabetta,Paradine, Shauna M.,Jacobsen, Eric N.
supporting information, p. 7272 - 7278 (2021/05/26)
We report a one-step catalytic, enantioselective method for the preparation of homoallylic N-Boc amines directly from acetals. Reactive iminium ion intermediates are generated in situ through the combination of an acetal, a chiral thiourea catalyst, trialkylsilyl triflate, and N-Boc carbamate and are subsequently trapped by a variety of allylsilane nucleophiles. No homoallylic ether byproducts are detected, consistent with allylation of the iminium intermediate being highly favored over allylation of the intermediate oxocarbenium ion. Acetals derived from aromatic aldehydes possessing a variety of functional groups and substitution patterns yield homoallylic amines with excellent levels of enantiomeric enrichment. Experimental and computational data are consistent with an anchoring hydrogen-bond interaction between the protioiminium ion and the amide of the catalyst in the enantiodetermining transition state, and with stereodifferentiation achieved through specific noncovalent interactions (NCIs) with the catalyst pyrenyl moiety. Evidence is provided that the key NCI in the major pathway is a π-stacking interaction, contrasting with the cation-πinteractions invoked in previously studied reactions promoted by the same family of aryl-pyrrolidino-H-bond-donor catalysts.