493-04-9Relevant academic research and scientific papers
Diverse and yet unified: A comparative study of the supramolecular assemblies of three diastereomeric perhydro-2,3,4a,6,7,8a-naphthalenehexols
Mehta, Goverdhan,Sen, Saikat
, p. 123 - 131 (2009)
Self-assemblies of three crystalline perhydro-2,3,4a,6,7,8a- naphthalenehexols 3-5, all constructed on a trans-decalin framework, were compared with each other and to that of their diastereomeric all axial hydroxy sibling 2, which was previously reported. The presence of the peripheral equatorial OH groups in 3-5 severs, to varying extents, the end-to-end intramolecular O-H...O hydrogen-bonding chain linking the 1,3-diaxial hydroxy groups on both faces of hexol 2. Hence, the crystal packing in 3-5 deviates from the simple qualitative model proposed and observed in 2. Though complex and seemingly individualistic upon a cursory glance, the supramolecular assemblies of all three hexols underscore two primary concepts of O-H...O hydrogen bonding, namely, maximization of the total number of hydrogen bonds per molecule and maximization of O-H...O hydrogen-bond cooperativity by forming as many finite and infinite chains of hydrogen bonds as possible. Wiley-VCH Verlag GmbH & Co. KGaA, 2009.
Non-Cryogenic, Ammonia-Free Reduction of Aryl Compounds
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, (2022/03/31)
A method of reducing an aromatic ring or a cyclic, allylic ether in a compound includes preparing a reaction mixture including a compound including an aromatic moiety or a cyclic, allylic ether moiety, an alkali metal, and either ethylenediamine, diethylenetriamine, triethylenetetramine, or a combination thereof, in an ether solvent; and reacting the reaction mixture at from ?20° C. to 30° C. for a time sufficient to reduce a double bond in the aromatic moiety to a single bond or to reduce the cyclic, allylic ether moiety.
Reduction method of electronic salt reaction liquid and unsaturated aromatic hydrocarbon compound
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Paragraph 0064-0067, (2021/11/10)
To the reduction method, tetrahydrofuran is used as a solvent and an electron trapping agent, metal lithium is used as a reducing agent, tertiary butanol is used as a reducing agent, and the unsaturated aromatic hydrocarbon compound is reduced under -10 - 0 °C conditions. The raw material tetrahydrofuran is used in the invention. Metal lithium and tert-butyl alcohol are all conventional chemical products, and are simple and easy to obtain. After the reaction is finished, excess lithium and solvent are recovered, and directly used to realize low cost, low pollution and high yield.
Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry
Peters, Byron K.,Rodriguez, Kevin X.,Reisberg, Solomon H.,Beil, Sebastian B.,Kawamata, Yu,Baran, Phil S.,Hickey, David P.,Klunder, Kevin,Gorey, Timothy J.,Anderson, Scott L.,Minteer, Shelley D.,Collins, Michael,Starr, Jeremy,Chen, Longrui,Udyavara, Sagar,Neurock, Matthew
, p. 838 - 845 (2019/04/30)
Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research in lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions for the Birch reduction. Specifically, we demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with a cheap, nontoxic, and water-soluble proton source (dimethylurea), and an overcharge protectant inspired by battery technology [tris(pyrrolidino)phosphoramide] can allow for multigram-scale synthesis of pharmaceutically relevant building blocks. We show how these conditions have a very high level of functional-group tolerance relative to classical electrochemical and chemical dissolving-metal reductions. Finally, we demonstrate that the same electrochemical conditions can be applied to other dissolving metal-type reductive transformations, including McMurry couplings, reductive ketone deoxygenations, and epoxide openings.
Novel electronic salt system and method for reducing unsaturated hydrocarbon compound
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Paragraph 0145-0149, (2018/09/08)
The invention discloses an electronic salt system and a method for reducing unsaturated hydrocarbon compounds by using the electronic salt system, belongs to the field of organic synthesis, and solvesthe problems such as complicated operation, harsh conditions, easy generation of complex over-reduction products of methods for reducing the unsaturated hydrocarbon compounds in the prior art. An electron salt may be synthesized by an alkali metal reagent, an ether and an alcohol, the ether can be a crown ether or a cryptand; and the method adopts the electronic salt system, the unsaturated hydrocarbon compounds is reduced by the electronic salt system in an organic solvent. The method for reducing the unsaturated hydrocarbon compounds is used for reducing the unsaturated hydrocarbon compounds.
Towards the enantioselective synthesis of (-)-euonyminol-preparation of a fully functionalised lower-rim model
Webber, Matthew J.,Warren, Sarah A.,Grainger, Damian M.,Weston, Matthew,Clark, Stacy,Woodhead, Steven J.,Powell, Lyn,Stokes, Stephen,Alanine, Alexander,Stonehouse, Jeffrey P.,Frampton, Christopher S.,White, Andrew J. P.,Spivey, Alan C.
supporting information, p. 2514 - 2533 (2013/06/05)
The development of a stereoselective total synthesis of β-dihydroagarofuran 4 is described. This compound contains the same oxygenation pattern on its 'lower-rim' as found in the natural sesquiterpene (-)-euonyminol (1) and it is expected that the route described should be applicable to the synthesis of that complex natural product. (-)-Euonyminol is found as the core scaffold of a series of complex macrodilactone sesquiterpenoids isolated from the Celastraceae which possess interesting biological activities (e.g. anti-HIV activity). The synthetic route builds upon an epoxidative asymmetric desymmetrisation of meso-diallylic alcohol 10 that we have reported previously. It features a lactate Ireland-Claisen rearrangement to establish the quaternary stereocentre at C11 (27 → 28a) and an unusual dealkylative intramolecular epoxide-opening by the C11 methyl ether to establish the tetrahydrofuranyl C-ring of the β-dihydroagarofuran skeleton (35 → 36). The Royal Society of Chemistry 2013.
Synthesis of anti-anti (anti-syn)-3,4:8,9-tetraacetoxy-11-oxa-tricyclo [4.4.1.01,6]undecanes
Kelebekli, Latif
experimental part, p. 94 - 97 (2011/07/07)
Synthesis of anti-anti-and anti-syn-3,4:8,9-tetraacetoxy-11-oxa-tricyclo[4. 4.1.01,6] undecanes have been achieved starting from naphthalene. The Birch reduction of naphthalene gave 1,4,5,8-tetrahydro-naphthalene in high yield. 1,4,5,8-Tetrahydro-naphthalene was selectively oxidised with mCPBA to give 11-oxa-tricyclo[4.4.1.01,6]undeca-3,8-diene. OsO4 oxidation followed by acetylation furnished the corresponding tetraacetates.
Desymmetrisation of bicyclo[4.4.0]decadienes: A planar-chiral complex proved to be most effective in an asymmetric Heck reaction
Lormann, Matthias E.P.,Nieger, Martin,Br?se, Stefan
, p. 2159 - 2161 (2007/10/03)
The synthesis and desymmetrisation of bicyclo[4.4.0]decadienes is described; the enantioselective Heck reaction using JOSIPHOS as a planar-chiral complex produces a tetracyclic system with three stereogenic centers in up to 84% enantiomeric purity.
Reductions with lithium in low molecular weight amines and ethylenediamine
Garst,Dolby,Esfandiari,Fedoruk,Chamberlain,Avey
, p. 7098 - 7104 (2007/10/03)
Reductions of several types of compounds with lithium and ethylenediamine using low molecular weight amines as solvent are described. In all cases 1 mol of ethylenediamine or N,N'-dimethylethylenediamine per gram-atom of lithium was used. In some cases it was beneficial to add an alcohol as a proton donor. These reaction conditions were applied to the debenzylation of N-benzylamide and lactams which are refractory to hydrogenolysis with hydrogen and a catalyst. N-Benzylpilolactam 2, synthesized from pilocarpine hydrochloride in refluxing benzylamine, was debenzylated in good yield using 10 gram-atoms of lithium per mole (10 Li/mol) of 2 in n-propylamine. The debenzylation of N-benzyl-N-methyldecanoic acid amide, 4 (6 Li/mol), in t-butylamine/N,N'-dimethylethylenediamine gave N-methyldecanoic acid amide 6 in 70% yield. Alternatively, reduction of 4 (7 Li/mol) in t-butanol/n-propylamine/ethylenediamine gave n-decanal 12 in 36% yield. Using the same conditions, thioanisole, 1-adamantane-p-toluenesulfonamide, and 1-adamantane methyl p-toluenesulfonate were reduced with 3, 7, and 7.2 Li/mol of compound to give thiophenol (74%), adamantamine (91%), and 1-adamantane methanol (75%), respectively. In this solvent system naphthalene and 3-methyl-2-cyclohexene-1-one were reduced to isotetralin (74%) and 3-methyl cyclohexanone (quantitative) with 5 and 2.2 Li/mol of starting compound, respectively. Oximes and O-methyloximes were reduced to their corresponding amines using 5 and 8 Li/mol of compound, respectively. Anisole was also reduced to 1-methoxy-1,4-cyclohexadiene with 2.5 Li/mol of anisole. Undecanenitrile was reduced to undecylamine with 8.6 Li/mol. Additionally, a base-catalyzed formation of imidazolines from a nitrile and ethylenediamine was also explored.
Lithium and amine dissolving metal reduction
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, (2008/06/13)
The invention is directed to a process for reducing or reductively cleaving an organic compound susceptible to dissolving metal reduction comprising exposing the organic compound to a solution of lithium in a polyamine including at least two amino groups, selected from the group consisting of primary and secondary amino groups and mixtures thereof, e.g. ethylenediamine and R--NH2, optionally containing a lower alkyl alcohol, wherein R is chosen from the group consisting of ethyl, propyl, and butyl, including all straight and branched chain isomers thereof, for a time sufficient to effect reduction.
