- Enantioselective Alkylamination of Unactivated Alkenes under Copper Catalysis
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An enantioselective addition reaction of various alkyl groups to unactivated internal alkenes under Cu catalysis has been developed. The reaction uses amide-linked aminoquinoline as the directing group, 4-alkyl Hantzsch esters as the donor of alkyl radicals, and rarely used biaryl diphosphine oxide as a chiral ligand. β-lactams featuring two contiguous stereocenters at Cβ and the β substituent can be obtained in good yield with excellent enantioselectivity. Mechanistic studies indicate that a nucleophilic addition of the alkyl radical to CuII-coordinated alkene is the enantio-determining step.
- Bai, Zibo,Zhang, Heng,Wang, Hao,Yu, Hanrui,Chen, Gong,He, Gang
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supporting information
p. 1195 - 1202
(2021/02/05)
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- Tandem IBX-Promoted Primary Alcohol Oxidation/Opening of Intermediate β,γ-Diolcarbonate Aldehydes to (E)-γ-Hydroxy-α,β-enals
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A tandem IBX-promoted oxidation of primary alcohol to aldehyde and opening of intermediate β,γ-diolcarbonate aldehyde to (E)-γ-hydroxy-α,β-enal has been developed. Remarkably, the carbonate opening delivered exclusively (E)-olefin and no over-oxidation of γ-hydroxy was observed. The method developed has been extended to complete the stereoselective total synthesis of both (S)- and (R)-coriolides and d-xylo- and d-arabino-C-20 guggultetrols.
- Kumari, Anupama,Gholap, Sachin P.,Fernandes, Rodney A.
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p. 2278 - 2290
(2019/06/17)
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- SULFAMATE DERIVATIVE COMPOUND FOR USE IN PREVENTING OR TREATING EPILEPSY
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The present invention relates to a pharmaceutical composition for treating or preventing epilepsy containing a sulfamate derivative compound and/or pharmaceutically acceptable salt thereof as an active ingredient. Furthermore, the present invention relates to a method for treatment or prevention epilepsy comprising administering a sulfamate derivative compound in a pharmaceutically effective amount to a subject in need of treatment or prevention of epilepsy.
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Page/Page column 124
(2015/06/25)
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- Nickel-Catalyzed Cross-Coupling of Anisoles with Alkyl Grignard Reagents via C-O Bond Cleavage
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Nickel-catalyzed cross-coupling of methoxyarenes with alkyl Grignard reagents, which involves the cleavage of the C(aryl)-OMe bond, has been developed. The use of 1,3-dicyclohexylimidazol-2-ylidene as a ligand allows the introduction of a variety of alkyl groups, including Me, Me3SiCH2, ArCH2, adamantyl, and cyclopropyl. The method can also be used for the alkylative elaboration of complex molecules bearing a C(aryl)-OMe bond.
- Tobisu, Mamoru,Takahira, Tsuyoshi,Chatani, Naoto
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supporting information
p. 4352 - 4355
(2015/09/15)
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- Distal-selective hydroformylation using scaffolding catalysis
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In hydroformylation, phosphorus-based directing groups have been consistently successful at placing the aldehyde on the carbon proximal to the directing group. The design and synthesis of a novel catalytic directing group are reported that promotes aldehyde formation on the carbon distal relative to the directing functionality. This scaffolding ligand, which operates through a reversible covalent bond to the substrate, has been applied to the diastereoselective hydroformylation of homoallylic alcohols to afford δ-lactones selectively. Altering the distance between the alcohol and the olefin revealed that homoallylic alcohols gives the distal lactone with the highest levels of regioselectivity.
- Joe, Candice L.,Blaisdell, Thomas P.,Geoghan, Allison F.,Tan, Kian L.
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supporting information
p. 8556 - 8559
(2014/07/07)
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- PHENYLALKYL SULFAMATE COMPOUND AND MUSCLE RELAXANT COMPOSITION COMPRISING THE SAME
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The present invention relates to novel phenylalkyl sulfamate compounds, a method for preventing or treating a disease associated with muscle spasm. The present invention ensures the enhancement of muscle relaxation activity essential for alleviation of muscle spasm, such that it is promising for preventing or treating various diseases associated with muscle spasm.
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Page/Page column 128-129
(2014/01/08)
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- Synthesis of allylic and homoallylic alcohols from unsaturated cyclic ethers using a mild and selective C-O reduction approach
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Unsaturated cyclic ethers can be mildly and selectively reduced with catalytic amounts of B(C6F5)3 in the presence of an alkylsilane. The allylic position is preferentially reduced with minimal or no scrambling of olefin geometry. For electronically equivalent substrates, steric factors guide the reducing agent to the least substituted site.
- MacK, Daniel J.,Guo, Boying,Njardarson, Jon T.
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supporting information; experimental part
p. 7844 - 7846
(2012/09/05)
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- Branched-regioselective hydroformylation with catalytic amounts of a reversibly bound directing group
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(Chemical Equation Presented) Phosphinites do the trick and work as reversibly bound catalyst-directing groups in catalytic amounts to allow for the highly regioselective hydroformylation of homo-allylic alcohols with terminal and internal alkene functions in favor of the branched product.
- Gruenanger, Christian U.,Breit, Bernhard
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supporting information; experimental part
p. 7346 - 7349
(2009/04/07)
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- COMPOUNDS WITH A HERBAL ODOR III. CIS-ALKENES WITH AN OXYGEN FUNCTION AT THE β POSITION AND THEIR SYNTHESIS BY HYDROGENATION OF DIENE PRECURSORS AT CHROMIUM HEXACARBONYL
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During the hydrogenation of dienes with oxygen functions at the α position in the presence of chromium hexacarbonyl 1,4-addition of hydrogen to the diene system occurs, and this leads to the corresponding cis-monoene derivatives.In the case of dienes with hydroxyl, alkoxyl, acetal, and ester groups the product yield approaches quantitative; the hydrogenation of similar oxo and acyloxy derivatives is less satisfactory.Many representatives of the synthesized compounds, in which the cis-disubstituted double bond is separated from the oxygen-containing functional group by two carbon atoms, have a herbal odor.
- Vasil'ev, A. A.,Cherkaev, G. V.
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p. 834 - 840
(2007/10/02)
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- SYNTHESIS OF HOMOALLYLIC ALCOHOLS VIA PALLADIUM-CATALYZED COUPLING OF ORGANOMERCURIALS AND VINYLIC OXETANES
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The reaction of aryl- and vinylmercurials, cupric chloride, 5percent aqueous NH4Cl, oxygen, catalytic amounts of Li2PdCl4 and vinylic oxetanes affords an excellent route to functionally-substituted homoallylic alcohols.
- Larock, Richard C.,Stolz-Dunn, Sandra K.
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p. 5069 - 5072
(2007/10/02)
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