1000-87-9Relevant articles and documents
-
Stang,P.J.,Hargrove,R.J.
, p. 657 - 658 (1975)
-
Pasto et al.
, p. 3496 (1976)
Synthesis and X-ray crystal structure of a cationic gold (I) π-(1,3-diene) complex generated via isomerization of a gold π-allene complex
Brown, Timothy J.,Robertson, Bradley D.,Widenhoefer, Ross A.
, p. 25 - 28 (2014/03/21)
The cationic gold tetramethylallene complex {[P(t-Bu)2o- biphenyl]Au(η2-Me2CCCMe2)}+ SbF6- (1) underwent formal 1,3-hydrogen migration in CD2Cl2 solution at
Competition of Mechanisms in Nucleophilic Substitution of Vinyl Halides. An Unequivocal Example of the Vinylic SRN1 Route
Galli, Carlo,Gentili, Patrizia,Rappoport, Zvi
, p. 6786 - 6795 (2007/10/02)
In a search for an unambiguous example of the vinylic SRN1 route, several vinyl bromides and iodides were reacted mostly with (-)CH2COCMe3, and sometimes with (-)CH2COPh, (-)CH(Me)COEt, and (EtO)2PO(-) ions, under Fe(2+)- or photostimulation in Me2SO.Vinyl halides having vinylic hydrogens, such as β-bromostyrene, gave acetylenic products, e.g., phenylacetylene or a tertiary PhCC-substituted alcohol, whereas vinyl halides with allylic hydrogens, such as Me2C=C(I)CHMe2, gave a substituted allene.Reduction products of the halogen, as well as substitution and rearranged substitution products, were also formed.The operation of ionic elimination-addition routes accounts for formation of most of the products, while the reduction products arise from an intermediate vinyl radical.Ph2C=C(Br)Ph (20) and Me2C=C(Br)Ph (25) gave both substitution and reduction products, but Me2C=C(Br)-t-Bu (23) gave only a reduction product.Formation of substitution products from the conjugated 20 and 25 was ascribed to a reaction via a vinylic SRN1 route, while lack of substitution in 23 is related to its nonconjugated system and to the consequent higher energy that the radical anion of the substitution product would have.The one here reported seems to be the first case of an exclusive genuine vinylic SRN1 process.
