3355-31-5Relevant articles and documents
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Caserio,Pratt
, p. 91 (1967)
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Synthesis of bicyclic N,N-enaminals by cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH
Gvozdev,Shavrin,Nefedov
, p. 2430 - 2437 (2014/11/08)
A cyclization of alk-4-ynals with aliphatic diamines in DMSO upon treatment with KOH was found to lead to bicyclic N,N-enaminals. The studies of this reaction showed that 1,3-diaminopropane and N-methyl-1,3-diaminopropane gave (E)-6-(arylmethylidene)octahydropyrrolo[1,2-a]pyrimidines in 45 - 78% yields, whereas 1,2-diaminoethane gave 5-(arylmethylidene)hexahydropyrrolo[1,2-a] imidazoles as mixtures of E- and Z-isomers in up to 75% total yield. The mechanism of these new cascade cyclization reactions includes formation of the equilibrium mixtures of imines and cyclic aminals with subsequent intramolecular hydroamination of the triple bond having considerable ionic character.
Copper(I)-catalyzed regio- and chemoselective single and double addition of nucleophilic silicon to propargylic chlorides and phosphates
Hazra, Chinmoy K.,Oestreich, Martin
supporting information; experimental part, p. 4010 - 4013 (2012/10/08)
Copper(I)-catalyzed propargylic substitution of linear precursors with (Me2PhSi)2Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me2PhSi) 2Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride (γ:α ≥ 99:1) where the propargylic displacement occurs quantitatively prior to the addition step. Substitutions of α-branched propargylic phosphates are also reported.