24767-80-4Relevant academic research and scientific papers
Evidence for concerted processes in the course of the homoallenylic transposition
Aouf, Chahinez,Galy, Nicolas,Santelli, Maurice
, p. 3225 - 3233 (2013/04/24)
The hydrolysis of β-allenic tosylates produces mainly 2-methylenecyclobutanols resulting from a homoallenylic participation along with isomeric 2-methylenecyclobutanol minor products coming from a 1234-1243 rearrangement. Structures of various cyclopropylvinyl carbocations involved in the course of the hydrolysis have been determined by computational studies. For acyclic tosylates, the hydrolysis of one β-deuterated allenic tosylate confirmed the nucleophilic attack on the corresponding nonclassical carbonium ion before its evolution to a more stable cyclopropylvinyl carbocation. In the case of one cyclic β-allenic tosylate, the structure of the products has been checked by the use of deuterated isotopomer.
Highly active Au(I) catalyst for the intramolecular exo- hydrofunctionalization of allenes with carbon, nitrogen, and oxygen nucleophiles
Zhang, Zhibin,Liu, Cong,Kinder, Robert E.,Han, Xiaoqing,Qian, Hua,Widenhoefer, Ross A.
, p. 9066 - 9073 (2007/10/03)
Reaction of benzyl (2,2-diphenyl-4,5-hexadienyl)carbamate (4) with a catalytic 1:1 mixture of Au[P(t-Bu)2(o-biphenyl)]CI (2) and AgOTf (5 mol %) in dioxane at 25 °C for 45 min led to isolation of benzyl 4,4-diphenyl-2-vinylpyrrolidine-1-carboxylate (5) in 95% yield. The Au(l)-catalyzed intramolecular hydroamination of N-allenyl carbamates tolerated substitution at the alkyl and allenyl carbon atoms and was effective for the formation of piperidine derivatives, γ-Hydroxy and δ-hydroxy allenes also underwent Au-catalyzed intramolecular hydroalkoxylation within minutes at room temperature to form the corresponding oxygen heterocycles in good yield with high exoselectivity. 2-Allenyl indoles underwent Au-catalyzed intramolecular hydroarylation within minutes at room temperature to form 4-vinyl tetrahydrocarbazoles in good yield. Au-catalyzed cyclization of N-allenyl carbamates, allenyl alcohols, and 2-allenyl indoles that possessed an axially chiral allenyl moiety occurred with transfer of chirality from the allenyl moiety to the newly formed stereogenic tetrahedral carbon atom.
