- Second-Generation palladium catalyst system for transannular C-H functionalization of azabicycloalkanes
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This article describes the development of a second-generation catalyst system for the transannular C-H functionalization of alicyclic amines. Pyridine- and quinoline-carboxylate ligands are shown to be highly effective for increasing the reaction rate, yield, and scope of Pd-catalyzed transannular C-H arylation reactions of azabicyclo[3.1.0]hexane, azabicyclo[3.1.1]heptane, azabicyclo[3.2.1]octane, and piperidine derivatives. Mechanistic studies reveal that the pyridine/quinoline-carboxylates play a role in impeding both reversible and irreversible catalyst decomposition pathways. These ligands enable the first reported examples of the transannular C-H arylation of the ubiquitous tropane, 7-azanorbornane, and homotropane cores. Finally, the pyridine/quinoline-carboxylates are shown to promote both transannular C-H arylation and transannular C-H dehydrogenation on a homotropane substrate.
- Cabrera, Pablo J.,Lee, Melissa,Sanford, Melanie S.
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supporting information
p. 5599 - 5606
(2018/05/03)
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- Synthesis and pharmacology of 6-substituted benztropines: Discovery of novel dopamine uptake inhibitors possessing low binding affinity to the dopamine transporter
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A series of 6α- and 6β-substituted benztropines were synthesized. A marked enantioselectivity was observed for the 6β-methoxylated benztropines, the (1R)-isomers being more potent than the corresponding (1S) compounds. The racemic 6α-methoxy-3-(4′,4″- dif
- Simoni, Daniele,Rossi, Marcello,Bertolasi, Valerio,Roberti, Marinella,Pizzirani, Daniela,Rondanin, Riccardo,Baruchello, Riccardo,Invidiata, Francesco Paolo,Tolomeo, Manlio,Grimaudo, Stefania,Merighi, Stefania,Varani, Katia,Gessi, Stefania,Borea, Pier Andrea,Marino, Silvia,Cavallini, Sabrina,Bianchi, Clementina,Siniscalchi, Anna
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p. 3337 - 3343
(2007/10/03)
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- Synthesis and analgesic activity of epibatidine analogues
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Two epibatidine analogues with different skeleton were synthesized and their analgesic activity was evaluated. Compound 2 which has the 8-azabicyclo[3.2.1]octane ring system showed potent analgesic activity in hot-plate assay.
- Xu,Bai,Chu,Tao,Zhu
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p. 279 - 282
(2007/10/03)
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- Synthesis of exo- and endo-6,7-epoxytropanes
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Diastereoisomeric N-protected 2,3-epoxy-4-amino-cycloheptanols are synthesised; cyclisation of derivatives provides a practical route to N-protected exo-(β)-6,7-epoxynortropanes and the first endo-(α-)-6,7-epoxynortropane. Hydride reduction gives the corr
- Justice, David E.,Malpass, John R.
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p. 11963 - 11976
(2007/10/03)
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- Exo- and Endo-6-Hydroxy- and 6,7-Epoxytropanes; Total Synthesis of Scopine, Pseudoscopine, and Nor- Derivatives
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Novel endo- 6,7-epoxy-8-azabicyclooctane derivatives and the corresponding exo-analogues have been synthesised and show substantially different reactivity; the resistance of the exo-epoxides to ring opening during hydride reduction and catalytic hydrogenolysis is exploited in a total synthesis of scopine, pseudoscopine, and nor- derivatives.
- Justice, David E.,Malpass, John R.
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p. 4689 - 4692
(2007/10/02)
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- Novel 6-substituted 8-azabicyclo [3.2.1.] octanes as potential opiate agonists and antagonists
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Reaction of 8-methyl-8-azabicyclo[3.2.1]octan-6-one (tropan-6-one) with aryl magnesium halides selectively yields 6β-aryl-6α-hydroxy-8-methyl-8-azabicyclo[3.2.1]octanes (6β-aryl-6α-hydroxytropanes). 1H nmr studies supporting the assignment are presented, together with 13C data of these alcohols and various derivatives prepared as potential agonists and antagonists of opiate receptors. The results from 1H nmr studies of 6-hydroxytropan-3-one, the synthesis of which was reported in 1952, support the assigned 6β-hydroxy stereochemistry.
- Dewar,Parfitt,Sheh
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p. 228 - 234
(2007/10/02)
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