Practical Preparation and Resolution of 1-(2‘-Diphenylphosphino-1‘-naphthyl)isoquinoline:  A Useful Ligand for Catalytic Asymmetric Synthesis

Lim, Chun Kyu; Tissot, Olivier; Mattison, Andrew; Hooper, Mark W.; Brown, John M.; Cowley, Andrew R.; Hulmes, David I.; Blacker, A. John

doi:10.1021/op034007n

Cited by 135 publications

(57 citation statements)

References 21 publications

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“…23 Cyclometalations that are assisted by oxygen, arsenic, and selenium donors are also known, though they are much rarer. 149,150 Chirality has been incorporated, for example through asymmetric ligand synthesis, [426][427][428][429][430] 436 Monomers are also present in solvents like benzene at high temperatures.…”

Section: Scheme 108mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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Section: Scheme 108mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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“…Azatriphenylenes are important in inorganic biochemistry thanks to their use as intercalating ligands [4,5]. In addition, azatriphenylenes have shown promise as luminescent chemosensors of organic anions and nitroaromatic compounds [6].…”

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Preparation of Pyridyl-substituted Monoazatriphenylenes

Kopchuk

Zyryanov

Коvalev

et al. 2013

Chem Heterocycl Comp

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Azatriphenylene derivatives are of considerable interest due to their promising photophysical and coordinating properties [1] and to their presence in the composition of natural compounds [2,3]. Azatriphenylenes are important in inorganic biochemistry thanks to their use as intercalating ligands [4,5]. In addition, azatriphenylenes have shown promise as luminescent chemosensors of organic anions and nitroaromatic compounds [6].The most frequently used method for preparing azatriphenylenes is the Skraup synthesis [7,8] which demands the use of forcing conditions. Contemporary synthetic methods broadly use a cycloaddition reaction of hard to obtain alkenes or arylacetylenes with aromatic substrates catalyzed by transition metal salts [9,10]. Finally, the cyclocondensation of phenanthrenequinone with hydrazones of (hetero)aromatic carboxylic acid amides leads to the corresponding aryl- [11,12] and hetaryl-substituted [13] triazatriphenylenes.In this report, we propose an efficient method for the synthesis of cycloalkene-annelated derivatives of monoazatriphenylenes based on an aza-Diels-Alder reaction of the previously uncharacterized 3-(pyridin-2-yl)phenathro[9,10-e][1,2,4]triazine (1) [14] with 1-morpholinocycloalkenes. A method for preparing different pyridine derivatives through reaction of the corresponding mononuclear 1,2,4-triazines has been known for some time [15][16][17]. In our work, we have used this method for the first time in a single-stage synthesis of the poorly available pyridyl-substituted monoazatriphenylenes 2a,b.

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“…alpha arylation | heterocycle | isoquinoline-N-oxide | one-pot T he isoquinoline motif and its derivatives form the cores of numerous natural products (1,2), are the central components of a number of pharmaceutical agents (3)(4)(5), and can provide the scaffold for chiral ligands (6,7) and valuable organic materials (8). However, traditional isoquinoline syntheses such as the Bischler-Napieralski (9, 10), Pictet-Spengler (11,12), and Pomeranz-Fritsch reactions (13)(14)(15) all centre around the lynchpin of electrophilic aromatic substitution and are thus often limited to electron-rich carbocycles (Scheme 1A).…”

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Synthesis of substituted isoquinolines utilizing palladium-catalyzed α-arylation of ketones

Donohoe

Pilgrim

Jones

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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The utilization of sequential palladium-catalyzed α-arylation and cyclization reactions provides a general approach to an array of isoquinolines and their corresponding N-oxides. This methodology allows the convergent combination of readily available precursors in a regioselective manner and in excellent overall yields. This powerful route to polysubstituted isoquinolines, which is not limited to electron rich moieties, also allows rapid access to analogues of biologically active compounds.T he isoquinoline motif and its derivatives form the cores of numerous natural products (1, 2), are the central components of a number of pharmaceutical agents (3-5), and can provide the scaffold for chiral ligands (6, 7) and valuable organic materials (8). However, traditional isoquinoline syntheses such as the Bischler-Napieralski (9, 10), 12), and Pomeranz-Fritsch reactions (13-15) all centre around the lynchpin of electrophilic aromatic substitution and are thus often limited to electron-rich carbocycles (Scheme 1A). It is also imperative to develop routes to highly-substituted isoquinolines to fully explore this chemical space, for example, for potential pharmaceutical targets. While recent synthetic efforts have greatly expanded the diversity of isoquinoline motifs available (16-29), new routes to isoquinolines are still highly desirable, particularly ones with the ability to directly access the isoquinoline moiety in a range of oxidation levels and which do not require highly-specialized starting materials.Originally reported by Palucki and Buchwald (30), Hamann and Hartwig (31), and Miura and coworkers (32), the palladiumcatalyzed α-arylation of enolates has recently emerged as a powerful new reaction in synthetic organic chemistry (33-35). Key to its success has been the design of appropriate ligands for palladium that have precisely engineered steric and electronic properties to enable the various steps in the catalytic cycle to proceed with maximum efficiency (36-39). The reaction's utility has also been greatly enhanced by the development of robust preformed palladium catalysts. Properties such as air stability and very high reactivity in a range of systems have greatly expanded the potential uses of these catalysts (40-43). However, the α-arylation reaction has seen limited use in the de novo construction of aromatic compounds (44-51) and is still greatly underused in this regard, especially because the bond forming abilities provided by this powerful reaction can greatly simplify the design of routes to heavily-substituted aromatic compounds. Hence, we decided to explore the scope of this new catalytic method in the synthesis of important heteroaromatic ring systems, beginning our investigations with the isoquinoline nucleus. ResultsIn our disconnection approach we envisaged that key pseudo-1,5-dicarbonyl intermediates 3 could be accessed via the palladiumcatalyzed α-arylation of ketones 1 with aryl halides 2 possessing a protected aldehyde or ketone in the ortho-position (52). Subsequent treatment of these inter...

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Practical Preparation and Resolution of 1-(2‘-Diphenylphosphino-1‘-naphthyl)isoquinoline: A Useful Ligand for Catalytic Asymmetric Synthesis

Cited by 135 publications

References 21 publications

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Preparation of Pyridyl-substituted Monoazatriphenylenes

Synthesis of substituted isoquinolines utilizing palladium-catalyzed α-arylation of ketones

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