- Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling
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Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.
- Neate, Peter G.N.,Zhang, Bufan,Conforti, Jessica,Brennessel, William W.,Neidig, Michael L.
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supporting information
p. 5958 - 5963
(2021/08/18)
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- Robust synthesis of NIR-emissive P-rhodamine fluorophores
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P-Rhodamines were accessed by implementing a robust three step sequence consisting of (i) addition of m-metallated anilines to dichlorophosphine oxides, (ii) selective dibromination, and (iii) cyclization of the diaryllithium reagents derived from the dib
- Arndt, Hans-Dieter,Nasufovic, Veselin,Sauer, Maria,Vilotijevic, Ivan
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supporting information
p. 1567 - 1571
(2020/03/06)
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- Nickel-catalyzed direct alkynylation of C(sp2)-H bonds of amides: An "inverse Sonogashira strategy" to ortho-alkynylbenzoic acids
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Nickel-catalyzed direct alkynylation of C(sp2)-H bonds of amides using commercially available, inexpensive 8-aminoquinoline as a removable bidentate directing group is described. The present ortho-alkynylation has a broad substrate scope, funct
- Landge, Vinod G.,Shewale, Chinmay H.,Jaiswal, Garima,Sahoo, Manoj K.,Midya, Siba P.,Balaraman, Ekambaram
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p. 1946 - 1951
(2016/04/05)
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- Lipase-mediated resolution of substituted 2-aryl-propanols: Application to the enantioselective synthesis of phenolic sesquiterpenes
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A comprehensive study of the lipase-mediated resolution of substituted 2-aryl-propanols is reported. The latter alcohols were submitted to the irreversible acetylation catalyzed either by PPL, CRL, or lipase PS. The enantioselectivity of these transformations was dependent on the type of lipase used. The type of substituents and particularly their position on the aromatic ring strongly affected the selectivity of the reaction. The experiments described prove that PPL is the more versatile lipase catalyzing the acetylation with an enantiomeric ratio (E) value that ranges from 1 up to 144, depending on the substrate used. Conversely, the same transformations were catalyzed by CRL and lipase PS with an enantiomeric ratio value, which is always less than 5. The remarkable behavior of PPL was exploited in the large scale resolution of some substituted 2-aryl-propanols whose enantiomeric forms are relevant building blocks in the enantioselective synthesis of phenolic sesquiterpenes. By these means, the synthesis of (S)-turmeronol B and the formal syntheses of (R)-curcumene, (R)-curcuphenol, (R)-xanthorrhizol, and (R)-curcuhydroquinone were accomplished.
- Serra, Stefano
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experimental part
p. 619 - 628
(2011/07/08)
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- ALPHA7 NICOTINIC ACETYLCHOLINE RECEPTOR INHIBITORS
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The present invention provides compounds and compositions, methods of making them, and methods of using them to modulate α7 nicotinic acetylcholine receptors and/or to treat any of a variety of disorders, diseases, and conditions. Provided compounds can a
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Page/Page column 63-64
(2010/04/03)
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- SYNTHESIS OF PYRAZOLES
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The present invention provides methods of making HCl salts, and methods of using them to modulate alpha7 nicotinic acetylcholine receptors and/or to treat any of a variety of disorders, diseases, and conditions. Provided compounds can affect, among other
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Page/Page column 46-47; 47-48
(2009/08/16)
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- NICOTINIC ACETYLCHOLINE RECEPTOR MODULATORS
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The present invention provides compounds of formula (I) and compositions thereof, methods of making them, and methods of using them to modulate alpha7 nicotinic acetylcholine receptors and/or to treat any of a variety of disorders, diseases, and conditions. Provided compounds can affect, among other things, neurological, psychiatric and/or inflammatory system.
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Page/Page column 47; 48
(2008/12/07)
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- Novel Rh catalysis in cross-coupling between alkyl halides and arylzinc compounds possessing ortho-COX (X = OR, NMe2, or Ph) groups
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Rh-dppf was found to be an efficient catalyst for the cross-coupling between primary alkyl halides bearings-hydrogens and arylzinc compounds possessing carbonyl groups such as ester, amide, or ketone at the ortho position. Various functional groups such as ester, nitrite, or acyloxylate moieties on the halides were tolerated under the catalysis conditions. Arylzinc compounds free of ortho-carbonyl groups reacted well with ethyl 3-iodopropanoate, suggesting that the essential intramolecular interaction between carbonyl groups and Rh promotes the reductive elimination.
- Takahashi, Hideki,Inagaki, Shinya,Nishihara, Yasushi,Shibata, Takanori,Takagi, Kentaro
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p. 3037 - 3040
(2007/10/03)
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- Negishi-type coupling of bromoarenes with dimethylzinc
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Treatment of bromoarenes with dimethylzinc in the presence of a palladium catalyst provides a high-yielding route to methylarenes. The process accommodates a wide range of aromatic substituents and, in the majority of cases, is free of side reactions.
- Herbert, John M.
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p. 817 - 819
(2007/10/03)
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- Protoberberins from Reissert Compounds VI [1]. Diastereoselective Synthesis and Relative Configuration of 2-Benzoyl-1-cyano-1-(1-phenylalkyl)-1,2-dihydroisoquinolines
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The alkylation of Reissert compounds 8 by sec-benzyl bromides 4, 7, and 10 diastereoselectively affords the title compounds 11 and 12. X-Ray structure analysis confirms an opposite configuration of the chiral centers in 11 and 12. The benzyl bromides 4, 7, and 10 are prepared by standard procedures.
- Reimann, Eberhard,Erdle, Wolfgang,Weigl, Claudia,Polborn, Kurt
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p. 313 - 326
(2007/10/03)
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- Photoreactivity of Conjugated Bichromophoric Molecules; Photoreaction of o-Vinylbenzaldehyde with Secondary Amines
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Irradiation of o-vinylbenzaldehyde 8 in the presence of secondary amines 9 results in N-H addition across the two chromophores to give o-ethylbenzamides 6; photolysis of o-(2-dialkylaminoethyl)benzaldehydes 5a and 5b also affords 6 via photoexpulsion followed by recombination of the 8 and 9 which are formed.
- Kessar, Satinder Vir,Mankotia, Anil K. Singh,Gujral, Gurjeet
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p. 840 - 841
(2007/10/02)
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- α,α-Dimethoxy-o-xylylene (5-(Dimethoxymethylene)-6-methylene-1,3-cyclohexadiene): Formation by 1,4-Elimination and Electrocyclic Routes and Reactions
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The title reactive intermediate 4, which features an unprecedented (Z)-alkoxy substituent, is generated in two independent ways.The ortho ester 5 undergoes 1,4-elimination on treatment with lithium diisopropylamide, at convenient rates in the temperature range 50-70 deg C.In the absence of added dienophile, 4 generated in this manner forms a spiro dimer and a dimer, both involving bonding between the two unsubstituted methylene groups.Diels-Alder adducts of 4 with norbornene (NB), norbornadiene, and cyclopentene are described.The ketal 8 formed from 4 and NB undergoes further 1,4-elimination, generating a new o-xylylene which in turn adds a second NB to yield the novel bis-adduct 11.Thermal opening of α,α-dimethoxybenzocyclobutene (6) is also used to generate 4.Rate constants for this reaction were determined over the temperature range 132-168 deg C, through the use of N-phenylmaleimide, which efficiently traps the intermediate, thereby preventing reclosure to 6 and other decomposition reactions.The Ea for this electrocyclic opening is 33.6 kcal/mol; comparative data from the literature are discussed.In the absence of a dienophile, 4 generated in this way recloses to 6 as its major reaction pathway but also undergoes an unusual rearrangement to form methyl o-ethylbenzoate (26).The overall rate of this reaction is ca. one-tenth that of the opening of 6 to 4 and restricts the range of dienophiles which can be used to trap 4 generated from 6.For example, even at the lowest temperature (132 deg C) needed to observe electrocyclic opening, and in the presence of a very large excess of NB, competitive cycloadduct formation and rearrangement to 26 are observed.Flash vacuum pyrolysis of 6 was also briefly examined.
- Moss, Randall J.,White, Russell O.,Rickborn, Bruce
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p. 5132 - 5139
(2007/10/02)
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- Substituted 9,10-dihydroanthracen-9,10-imines
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Substituted 9,10-dihydroanthracen-9,10-imines are disclosed to be minor tranquilizers, anticonvulsnts, muscle relaxants, and to be useful in the treatment of extrapyramidal disorders such as Parkinson's disease; also disclosed are processes for the preparation of such compounds; pharmaceutical compositions comprising such compounds; and methods of treatment comprising administering such compounds and compositions.
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