19482-57-6Relevant articles and documents
Alkylation of Terminal Alkynes under Zinc Lewis Acid Catalysis and Its Mechanistic Studies
Osano, Mana,Kida, Takeru,Yonekura, Kyohei,Tsuchimoto, Teruhisa
supporting information, p. 2825 - 2831 (2019/04/13)
With a zinc Lewis acid catalyst and proton sponge in toluene, terminal alkynes were found to undergo the alkylation by alkyl triflates to provide unsymmetrical internal alkynes. This is the first example that a simple alkyl chain other than benzylic and norbornyl units can be introduced onto the alkynyl carbon atom under Lewis acid catalysis. Mechanistic studies revealed that the activation of the alkyne by the zinc Lewis acid and proton sponge is the trigger of the reaction to give a monoalkynylzinc species, which successively reacts with the alkyl triflate to afford the internal alkyne. A radical pathway is unlikely in this system. (Figure presented.).
Arylsulfonylacetylenes as alkynylating reagents
Marzo, Leyre,Aleman, Jose,Garcia Ruano, Jose Luis
, p. 403 - 407 (2013/07/26)
The unexpected anti-Michael addition of RLi to β-substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp2) and C(sp3). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).
Propargylic oxidations catalyzed by dirhodium caprolactamate in water: Efficient access to α,β-acetylenic ketones
McLaughlin, Emily C.,Doyle, Michael P.
, p. 4317 - 4319 (2008/09/20)
(Chemical Equation Presented) Dirhodium(II) caprolactamate (1, Rh 2(cap)4) with 70% w/w aqueous tert-butyl hydroperoxide (T-HYDRO) is a highly effective catalytic oxidation protocol for the selective C-H oxidation of alkynes to propargylic ketones. The oxidation occurs readily in aqueous solvent under mild conditions with an inexpensive and easily handled oxidant. α,β-Acetylenic carbonyl compounds are formed in up to 80% isolated yield.