- Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion
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The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated"C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
- Modak, Atanu,Alegre-Requena, Juan V.,De Lescure, Louis,Rynders, Kathryn J.,Paton, Robert S.,Race, Nicholas J.
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supporting information
p. 86 - 92
(2021/12/27)
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- Iodine-Catalyzed Synthesis of Substituted Furans and Pyrans: Reaction Scope and Mechanistic Insights
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Substituted pyrans and furans are core structures found in a wide variety of natural products and biologically active compounds. Herein, we report a practical and mild catalytic method for the synthesis of substituted pyrans and furans using molecular iodine, a simple and inexpensive catalyst. The method described is performed under solvent-free conditions at an ambient temperature and atmosphere, thus offering a facile and practical alternative to currently available reaction protocols. A combination of experimental studies and density functional theory calculations revealed interesting mechanistic insights into this seemingly simple reaction.
- Pace, Domenic P.,Robidas, Rapha?l,Tran, Uyen P. N.,Legault, Claude Y.,Nguyen, Thanh Vinh
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p. 8154 - 8171
(2021/06/28)
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- BENZOQUINOLINE INHIBITORS OF VESICULAR MONOAMINE TRANSPORTER 2
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The present invention relates to new benzoquinoline inhibitors of vesicular monoamine transporter 2 (VMAT2), pharmaceutical compositions thereof, and methods of use thereof.
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Paragraph 0246; 0247
(2018/07/05)
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- A distinctive transformation based diversity oriented synthesis of small ring carbocycles and heterocycles from biocatalytically derived enantiopure α-substituted-β-hydroxyesters
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A series of structurally novel small ring carbocyclic and heterocyclic molecules were accessed in an enantiopure fashion. The starting materials, α-substituted-β-hydroxyesters, were achieved through the biocatalytic dynamic kinetic resolution of parent β-
- Halder, Joydev,Das, Debabrata,Nanda, Samik
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p. 2549 - 2575
(2018/04/12)
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- BENZOQUINOLONE INHIBITORS OF VMAT2
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The present invention relates to new benzoquinolone inhibitors of VMAT2, pharmaceutical compositions thereof, and methods of use thereof represented by structural Formula I.
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Paragraph 00107
(2015/04/15)
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- METHODS OF TREATING ABNORMAL MUSCULAR ACTIVITY
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Methods for treating abnormal muscular activity are disclosed. The methods may be performed remotely and permit monitoring of a subject outside a healthcare provider's office.
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Paragraph 0206
(2015/06/08)
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- BENZOQUINOLINE INHIBITORS OF VESICULAR MONOAMINE TRANSPORTER 2
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The present invention relates to new benzoquinoline inhibitors of vesicular monoamine transporter 2 (VMAT2), pharmaceutical compositions thereof, and methods of use thereof. (I)
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Paragraph 00174
(2015/06/08)
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- BENZOQUINOLINE INHIBITORS OF VESICULAR MONOAMINE TRANSPORTER 2
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The present invention relates to new benzoquinoline inhibitors of vesicular monoamine transporter 2 (VMAT2), pharmaceutical compositions thereof, and methods of use thereof. (Formula (I))
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Paragraph 00200
(2015/08/06)
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- Three-step synthetic pathway to fused bicyclic hydantoins involving a selenocyclization step
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Sequential 5-alkenyl hydantoin and pyrrolidine ring-forming reactions have been applied in the synthesis of conformationally constrained fused bicyclic scaffold. They are assembled by a three-step reaction sequence from two variable building blocks (readily available β-ketoesters and alkenyl halides) by combining a Bucherer-Bergs reaction with a final selenium-promoted intramolecular cyclization as a key step. The chemoselectivity of this bicyclic hydantoin formation is strongly influenced by experimental factors such as the solvent and the use of additives. The reaction is regiospecific giving only five-membered fused bicyclic hydantoins in good to excellent yields stemming from the nucleophilic attack of the nitrogen atom to a cyclic seleniranium ion intermediate during the cyclization step. A separable diastereomeric mixture is obtained; the products with bridgehead substituents and phenylseleno groups in cis relationships were formed predominantly. The reaction tolerates a variety of substitution at the double bond, furthermore, the presence of substituents at C(5) and N(3) position opens up the capability of generating a broad structural diversity.
- ?mit, Biljana M.,Pavlovi?, Radoslav Z.
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p. 1101 - 1108
(2015/01/30)
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- Dual platinum and pyrrolidine catalysis in the direct alkylation of allylic alcohols: Selective synthesis of monoallylation products
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A dual platinum- and pyrrolidine-catalyzed direct allylic alkylation of allylic alcohols with various active methylene compounds to produce products with high monoallylation selectivity was developed. The use of pyrrolidine and acetic acid was essential, not only for preventing undesirable side reactions, but also for obtaining high monoallylation selectivity. Two cats are better than one: The combined use of platinum and pyrrolidine catalysts enabled the direct alkylation of allylic alcohols with reactive methylene compounds. Pyrrolidine was essential for obtaining high selectivity of the monoallylation products, which were produced without the use of excess nucleophiles. cod=1,5- cyclooctadiene, EWG=electron-withdrawing group.
- Shibuya, Ryozo,Lin, Lu,Nakahara, Yasuhito,Mashima, Kazushi,Ohshima, Takashi
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supporting information
p. 4377 - 4381
(2014/05/06)
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- Efficient allylation of nucleophiles catalyzed by a bifunctional heterogeneous palladium complex-tertiary amine system
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We demonstrate the synergistic catalysis of a silica-supported diaminopalladium complex and a tertiary amine (SiO2/diamine/Pd/ NEt2) as well as synthetic scope of the Tsuji-Trost reaction of 1,3-dicarbonyls, phenols, and carboxylic acids with allyl carbonate and acetates. The synergistic catalysis of SiO2/diamine/Pd/NEt 2 exhibited wide applicability and high activity for the Tsuji-Trost reaction. For example, the reaction of ethyl 3-oxobutanate with allyl methyl carbonate afforded the allylated product in >99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO2/diamine/Pd, without immobilization of the tertiary amine group. In the reaction of 1.0 mmol of ethyl 3-oxobutanate using 0.60 μmol of Pd in SiO2/diamine/Pd/NEt 2, the turnover number (TON) of Pd reached up to 1070 within 24 h. Phenols with electron-withdrawing groups, such as nitro and chloro groups, on the para position resulted in high product yields. The SiO2/diamine/ Pd/NEt2 catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of p-chlorophenol. Copyright
- Noda, Hiroto,Motokura, Ken,Miyaji, Akimitsu,Baba, Toshihide
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p. 973 - 980
(2013/05/08)
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- CALCILYTIC COMPOUNDS
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Novel calcilytic compounds, pharmaceutical compositions, methods of synthesis and methods of using them are provided.
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Page/Page column 40
(2008/06/13)
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- Selenocyclofunctionalization of β-ketoamides: Synthesis of substituted dihydrofurans
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Selenocyclofunctionalization of α-substituted β-ketoamides obtained from the aminolysis of the ethyl acetoacetate yielded dihydrofurans in moderate to good yields.
- Stefani, Hélio A.,Costa, Iguatemi M.,De O. Silva, Diogo,Menezes, Paulo H.,Rodrigues, Alessandro
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p. 141 - 152
(2007/10/03)
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- Oxovanadium-induced or -catalyzed oxidative allylation of 1,3-dicarbonyl compounds with allylsilanes
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The oxidative mono- or di-allylation reaction of 1,3-dicarbonyl compounds with allylsilanes was selectively achieved by treatment with VO(OEt)Cl2.
- Hirao,Sakaguchi,Ishikawa,Ikeda
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p. 2579 - 2585
(2007/10/02)
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- Tetralin formate ester aroma chemicals
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The present invention relates to novel formate ester tetralin compounds having fragrant musk-like aroma.
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- SYNTHESIS OF ENOL ESTERS AND ENOL LACTONES VIA PALLADIUM-CATALYZED CARBONYLATION OF ARYL AND ALKENYL HALIDES
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Acylpalladium species derivable via oxidative addition of a Pd-phosphine complex with aryl and alkenyl iodides and CO insertion can react, either intramolecularly or intermolecularly, with enolates generated in situ to give the corresponding enol esters a
- Shimoyama, Izumi,Zhang, Yantao,Wu, Guangzhong,Negishi, Ei-ichi
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p. 2841 - 2844
(2007/10/02)
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- CHELATION-CONTROLLED CYCLIZATION OF β-KETOESTER-SUBSTITUTED AND β-KETOAMIDE-SUBSTITUTED ALLYLSILANES.
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The first examples of Lewis acid-catalyzed chelation-controlled cyclization reactions are reported.Titanium tetrachloride-initiated cyclization of β-ketoester and β-ketoamide-substituted allylsilanes proceeds in isolated yields of 65-88percent, providing
- Molander, Gary A.,Andrews, Steven W.
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p. 3115 - 3118
(2007/10/02)
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- SUBSTITUTIONS CATALYSEES AU NICKEL D'ACETATES ET DE SULFONES ALLYLIQUES
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The allylic substitution of stable enolates derived from diethyl malonate, ethyl cyanoacetate, ethyl benzylsulfonylacetate, bis(benzenesulfonyl)methane and sodium p-toluenesulfinate by a variety of allylic esters and sulfones has been investigated.Suitable ligands and reaction conditions have been found to ensure high yields, and in some cases considerable control of the regioselectivity of the reaction.
- Cuvigny, Therese,Julia, Marc
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p. 383 - 408
(2007/10/02)
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- STEREOSELECTIVE TOTAL SYNTHESIS OF RACEMIC GRANDISOL. AN IMPROVED CONVENIENT PROCEDURE
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(+/-) Grandisol has been stereoselectively synthesized in a 31 percent overall yield by a practical and convenient procedure employing the Salomon photobicyclization as the key-step.
- Rosini, Goffredo,Marotta, Emanuela,Petrini, Marino,Ballini, Roberto
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p. 4633 - 4638
(2007/10/02)
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- Organic Photochemistry with 6.7-ev Photons: γ,δ-Unsaturated Ketones
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The photochemistry of a series of acyclic, aliphatic γ,δ-unsaturated ketones in pentane solution with 185-nm light has been investigated.The variety of products formed can be rationalized as arising from discrete reactions of the individually excited chromophores.Neither intramolecular energy transfer nor internal conversion leading to population of the lowest (n,?*) singlet state are competitive with product formation at 185 nm.The mechanism of alkyne formation in the solution-phase photolysis of these and terminal alkenes at 185 nm is elucidated by using a deuterated derivative, and the reaction is postulated to proceed from the olefinic ?,?* singlet state.
- Leigh, William J.,Srinivasan, R.
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p. 4424 - 4429
(2007/10/02)
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