6836-98-2Relevant articles and documents
Remarkable aromatic substitution by a 1,5-diradical
Merkley, Nadine,Reid, Darren L,Warkentin, John
, p. 1927 - 1929 (2002)
Generation of 2,6-dioxa-3-phenylcyclohexylidene in benzene leads to 2,4-diphenyl-1,3-dioxane, the product of apparent insertion into a CH bond of benzene. However, that product arises from attack of a diradical intermediate on benzene.
A method for synthesizing γ-butaneol using 3,4-epoxy-1-butanol
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Paragraph 0033-0037, (2022/03/27)
The present invention provides a method of synthesizing γ - butyrolactone using 3,4-epoxy-1-butanol, 3,4-epoxy-1-butanol as raw material, under the catalysis of nickel and phosphine ligands and under the action of alkali, heating reaction in an organic solvent to give γ - butyrolactone. The present invention has the advantages of easy raw materials, easy operation, good adaptability, etc., the resulting γ - butyrolactone can be applied to the synthesis of pharmaceutical intermediates, natural products, polymers and the like.
Scope, Limitations and Mechanistic Analysis of the HyperBTM-Catalyzed Acylative Kinetic Resolution of Tertiary Heterocyclic Alcohols**
Smith, Samuel M.,Greenhalgh, Mark D.,Feoktistova, Taisiia,Walden, Daniel M.,Taylor, James E.,Cordes, David B.,Slawin, Alexandra M. Z.,Cheong, Paul Ha-Yeon,Smith, Andrew D.
supporting information, (2021/11/16)
The full scope and limitations of the catalytic acylative kinetic resolution of a range of tertiary heterocyclic alcohols (78 examples, s up to >200) is reported under operationally-simple conditions, using low loadings of a commercially available Lewis basic isothiourea catalyst, HyperBTM (generally 1 mol %). The protocol is highly effective for the kinetic resolution of 3-substituted 3-hydroxyoxindole and α-substituted α-hydroxylactam derivatives bearing up to three potential recognition motifs at the stereogenic tertiary carbinol center. The full power of this methodology has been showcased through the synthesis of highly enantioenriched biologically-active target compounds in both enantiomeric forms. To provide further insight into the reaction mechanism, a detailed kinetic analysis of this Lewis base-catalyzed acylation of tertiary alcohols is reported using the variable time normalization analysis (VTNA) method.
Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides
Li, Zijian,Sun, Wenxuan,Wang, Xianxu,Li, Luyang,Zhang, Yong,Li, Chao
supporting information, p. 3536 - 3543 (2021/03/08)
As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C-C bonds. Here, we demonstrate that the combination of anodic preparation of the alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)-C(sp3) bonds, in which free alcohols and aryl bromides - both readily available chemicals - can be directly used as coupling partners. This nickel-catalyzed paired electrolysis reaction features a broad substrate scope bearing a wide gamut of functionalities, which was illustrated by the late-stage arylation of several structurally complex natural products and pharmaceuticals.
Identification of Bond-Weakening Spirosilane Catalyst for Photoredox α-C?H Alkylation of Alcohols
Sakai, Kentaro,Oisaki, Kounosuke,Kanai, Motomu
supporting information, p. 337 - 343 (2019/12/24)
The development of catalyst-controlled site-selective C(sp3)?H functionalization is a current major challenge in organic synthesis. This paper describes DFT-guided identification of pentavalent silicate species as a novel bond-weakening catalyst for the α-C?H bonds of alcohols together with a photoredox catalyst and a hydrogen atom transfer catalyst. Specifically, Martin's spirosilane accelerated α-C?H alkylation of alcohols. (Figure presented.).
Platinum-on-Carbon-Catalyzed Aqueous Oxidative Lactonization of Diols by Using Molecular Oxygen
Ban, Kazuho,Sajiki, Hironao,Sawama, Yoshinari,Takakura, Ryoya
supporting information, p. 1919 - 1923 (2019/09/30)
A lactonization of various diols catalyzed by platinum on carbon (Pt/C) in water under an atmosphere of molecular oxygen was developed. Derivatives of 1,4- 1,5- and 1,6-diols were transformed into the corresponding five-, six-, and seven-membered lactones by the present oxidative lactonization method.
Structure and thermal reactivity of some 2-substituted 1,3-oxathiolane S-oxides
Aitken, R. Alan,Henderson, Sarah,Slawin, Alexandra M. Z.
, p. 422 - 434 (2018/03/26)
Isomerization of 2-benzylidene-1,3-dioxolane to 3-phenylbutyrolactone occurs readily under flash vacuum pyrolysis (FVP) conditions. 2-Diphenylmethyl-1,3-oxathiolane and 2-benzyl-1,3-oxathiolane have been prepared and the latter compound has been oxidized to the corresponding sulfoxide, whose structure and conformation are examined by 1H NMR, and to the sulfone whose X-ray structure is determined. 2-Benzylidene-1,3-oxathiolane is also prepared and the behavior of the three S-oxidized oxathiolane derivatives upon FVP is examined. While extrusion of SOn to give ethene and a carbonyl compound predominates in all three cases, the sulfoxide gives also bis(2-hydroxyethyl) disulfide, most likely formed via thiirane S-oxide and 1,2-oxathietane.
A palladium-catalyzed asymmetric allylic alkylation approach to α-quaternary γ-butyrolactones
De Oliveira, Marllon Nascimento,Fournier, Jeremy,Arseniyadis, Stellios,Cossy, Janine
supporting information, p. 14 - 17 (2017/11/27)
The Pd-catalyzed asymmetric allylic alkylation (Pd-AAA) of enol carbonates derived from γ-butyrolactones is reported, affording the corresponding enantioenriched α,α′-disubstituted γ-butyrolactones in both high yields and high enantioselectivities (up to 94% ee). This method was eventually applied to the synthesis of chiral spirocyclic compounds.
Lewis Acid Catalyzed Synthesis of α-Trifluoromethyl Esters and Lactones by Electrophilic Trifluoromethylation
Katayev, Dmitry,Matou?ek, Václav,Koller, Raffael,Togni, Antonio
supporting information, p. 5898 - 5901 (2015/12/11)
An electrophilic trifluoromethylation of ketene silyl acetals (KSAs) by hypervalent iodine reagents 1 and 2 has been developed. The reaction proceeds under very mild conditions in the presence of a catalytic amount of trimethylsilyl bis(trifluoromethanesulfonyl)imide (up to 2.5 mol %) as a Lewis acid providing a direct access to a variety of secondary, tertiary, and quaternary α-trifluoromethyl esters and lactones in high yield (up to 98%).
Dehydrogenative lactonization of diols in aqueous media catalyzed by a water-soluble iridium complex bearing a functional bipyridine ligand
Fujita, Ken-Ichi,Ito, Wataru,Yamaguchi, Ryohei
, p. 109 - 112 (2014/01/23)
A new catalytic system for the dehydrogenative lactonization of a variety of benzylic and aliphatic diols in aqueous media was developed. By using a water-soluble, dicationic iridium catalyst bearing 6,6′-dihydroxy-2, 2′-bipyridine as a functional ligand, highly atom economical and environmentally benign synthesis of various lactones was achieved in good to excellent yields. Recovery and reuse of the catalyst were also accomplished by a simple phase separation and the recovered catalyst maintained its high activity at least until the fifth run. Copyright
