2007
DOI: 10.1021/jo701591e
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Mercury(II) Triflate-Catalyzed Cycloisomerization of Allenynes to Allenenes

Abstract: Cycloisomerizations of allenynes to allenenes have been studied in the presence of catalytic amounts of [Hg(OTf)2] in acetonitrile. The catalytic system is quite effective for terminal 1,6-allenynes: allenenes were obtained in reasonable to high yields. However, treatment of allenynes with disubstituents at the allenic terminal carbon yielded a triene and/or allenene as a major product(s) depending upon the substituents.

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Cited by 23 publications
(5 citation statements)
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“…We propose that the reaction is likely to be initiated from a π-complex 9 . , Friedel−Crafts type cyclization leads to carbocation 10 , and the organomercuric intermediate 11 is produced by deprotonation. Protonation of the hydroxyl moiety of 11 by in situ generated TfOH leads to oxonium cation 12 .…”
mentioning
confidence: 97%
See 1 more Smart Citation
“…We propose that the reaction is likely to be initiated from a π-complex 9 . , Friedel−Crafts type cyclization leads to carbocation 10 , and the organomercuric intermediate 11 is produced by deprotonation. Protonation of the hydroxyl moiety of 11 by in situ generated TfOH leads to oxonium cation 12 .…”
mentioning
confidence: 97%
“…The reaction involves protonation of the alkenyl mercury intermediate 3 with in situ formed TfOH to generate cation 4 . Subsequent smooth demercuration leads to 2 and the regenerated catalyst. , Hg(OTf) 2 was originally developed in 1983 as an efficient olefin cyclization agent, and the reaction of farnesyl sulfone 5 with 1.2 equiv of Hg(OTf) 2 •PhNMe 2 afforded bicyclic product 6 in 74% yield . Because the latter reaction produces stable organomercuric product 6 , it is essentially a stoichiometric reaction .…”
mentioning
confidence: 99%
“…In a Hg(OTf) 2 -catalyzed process, 1,6-allenynes 158 were cycloisomerized to generate allenenes 159 in moderate to good yield ( Scheme 46 ) [ 105 ]. However, depending on the substituents, allenene and/or unexpected triene were produced as a main product for disubstituted 1,6-allenynes.…”
Section: Reviewmentioning
confidence: 99%
“…The stereochemistry of the chiral amino acid was not conserved in the cyclized product hence it leads to the formation of racemic products with moderate yields (Scheme 44). In a Hg(OTf) 2 -catalyzed process, 1,6-allenynes 158 were cycloisomerized to generate allenenes 159 in moderate to good yield (Scheme 46) [105]. However, depending on the substituents, allenene and/or unexpected triene were produced as a main product for disubstituted 1,6-allenynes.…”
Section: Cyclization Involving Catalytic Hg(ii) Salts Cyclization Involving Alkenes (>C=c<)mentioning
confidence: 99%
“…We initiated the study with the reaction of allenyne 1a 70–89 and B 2 (pin) 2 2a in the presence of MeOH with NaO t Bu as the base and CuCl (5 mol%) and Biphep ( L 1 ) (6 mol%) as the catalyst at 30 °C in THF for 16 h. To our delight, the 2,5-addition product, 1,3,4-trienyl boronate 3aa , was formed in 33% yield with 3% yield of the 2,3-addition product, 1,4-enyne 3aa′ (entry 1, Table 1). Upon adjusting the ratio of 1a / 2a to 1/1, a much higher yield of the desired product 3aa was achieved (entries 2–5, Table 1).…”
mentioning
confidence: 99%