- Intermolecular Phosphite-Mediated Radical Desulfurative Alkene Alkylation Using Thiols
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We report herein the development of a S atom transfer process using triethyl phosphite as the S atom acceptor that allows thiols to serve as precursors of C-centered radicals. A range of functionalized and electronically unbiased alkenes including those containing common heteroatom-based functional groups readily participate in this reductive coupling. This process is driven by the exchange of relatively weak S-H and C-S bonds of aliphatic thiols for C-H, C-C, and S-P bonds of the products formed.
- Lopp, John M.,Schmidt, Valerie A.
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p. 8031 - 8036
(2019/10/19)
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- Photoredox Reaction of 2-Mercaptothiazolinium Salts with Silyl Enol Ethers
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A method for the generation of free radicals from thiazolinium salts upon photocatalytic reduction is described. The thiazolinium salts are generated by treatment with methyl triflate of 2-mercaptothiazolines, which can be readily obtained from alkyl bromides and tosylates via a nucleophilic substitution reaction or by hydrothiolation of alkenes. Silyl enol ethers were used to trap the radicals, furnishing ketones after successive single-electron oxidation and elimination of the silyl cation.
- Zemtsov, Artem A.,Ashirbaev, Salavat S.,Levin, Vitalij V.,Kokorekin, Vladimir A.,Korlyukov, Alexander A.,Dilman, Alexander D.
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- Tandem intramolecular carbolithiation-transmetallation: From lithium to copper or boron chemistry
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Lithium/copper transmetallation from the organolithium intermediate 3 (obtained via intramolecular carbolithiation of the acyclic organolithium 2, generated by a chlorine-lithium exchange) gives the corresponding organocopper intermediate 5. This intermediate reacts with eletrophiles, such as allylic or propargylic halides, acyl chlorides or α,β-unsaturated carbonyl compounds giving the expected compounds 6-10, which are not possible to be obtained directly from the organolithium 3. On the other hand, lithium/boron transmetallation affords the corresponding alkylboronic acid 11 which, after palladium-catalysed Suzuki-Miyaura cross-coupling reaction with different aryl bromides gives the expected products 12 with modest yields, the corresponding Ullman biarylic homocoupling products being the major by-products.
- Ortiz, Rosa,Yus, Miguel
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p. 1699 - 1707
(2007/10/03)
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- Tandem intramolecular carbolithiation-lithium/zinc transmetallation and applications to carbon-carbon bond-forming reactions
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Lithium/zinc transmetallation with the cyclic organolithium intermediate 3 (prepared by intramolecular carbolithiation of the initially formed organolithium 2) gives the corresponding organozinc intermediate 5. Copper- or palladium-promoted SN2
- Yus, Miguel,Ortiz, Rosa
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p. 3833 - 3841
(2007/10/03)
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