764-60-3Relevant articles and documents
Synthesis of α,β-unsaturated epoxy ketones utilizing a bifunctional sulfonium/phosphonium ylide
Eskandari, Roozbeh,Hess, Jeremy P.,Tochtrop, Gregory P.
supporting information, p. 7136 - 7139 (2021/07/28)
Herein, a new protocol for rapid synthesis of α,β-unsaturated epoxy ketones utilizing a bifunctional sulfonium/phosphonium ylide is described. This approach comprises two sequential chemoselective reactions between sulfonium and phosphonium ylides and two distinct aldehydes, which allows for the rapid construction of a variety of unsymmetric α,β-unsaturated epoxy ketones. This methodology allows the rapid construction of the core reactive functionality of a family of lipid peroxidation products, the epoxyketooctadecenoic acids, but can be further broadly utilized as a useful synthon for the synthesis of natural products, particularly those derived from oxidized fatty acids. Accordingly, a protocol utilizing this approach to synthesize the epoxyketooctadecenoic acid family of molecules is described.
Enantioselective Rhodium-Catalyzed Dimerization of ω-Allenyl Carboxylic Acids: Straightforward Synthesis of C2-Symmetric Macrodiolides
Steib, Philip,Breit, Bernhard
supporting information, p. 6572 - 6576 (2018/05/08)
Herein, we report on the first enantioselective and atom-efficient catalytic one-step dimerization method to selectively transform ω-allenyl carboxylic acids into C2-symmetric 14- to 28-membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards multiple naturally occuring homodimeric macrocyclic scaffolds and demonstrates excellent efficiency to construct the complex, symmetric core structures. By utilizing a rhodium catalyst with a modified chiral cyclopentylidene-diop ligand, the desired diolides were obtained in good to high yields, high diastereoselectivity, and excellent enantioselectivity.
Gold(III)-Catalyzed Regioselective Oxidation/Cycloisomerization of Diynes: An Approach to Fused Furan Derivatives
Li, Jian,Xing, Hong-Wen,Yang, Fang,Chen, Zi-Sheng,Ji, Kegong
supporting information, p. 4622 - 4626 (2018/08/07)
The first gold(III)-catalyzed regioselective oxidation/cycloisomerization of diynes 1 with pyridine N-oxide as the oxidant was developed, providing a range of synthetically valuable and useful fused furan derivatives 3 in moderate to good yields. Control experiments and the confirmation structure of minor products 5 suggest that this chemistry was a concerted gold(III)-catalyzed oxidation/SN2′-type addition/cyclization process via a β-gold vinyloxypyridinium intermediate and a putative vinyl cation intermediate.
Sodium Phenoxide Mediated Hydroxymethylation of Alkynylsilanes with N-[(Trimethylsiloxy)methyl]phthalimide
Asano, Narumi,Sasaki, Keita,Chataigner, Isabelle,Shigeno, Masanori,Kondo, Yoshinori
supporting information, p. 6926 - 6930 (2017/12/26)
The hydroxymethylation of alkynylsilanes with formaldehyde generated in situ from N-[(trimethylsiloxy)methyl]phthalimide proceeds in the presence of a stoichiometric amount of NaOPh. The reaction occurs at room temperature by using an operationally simple one-step procedure. A variety of alkynylsilanes possessing electron-donating, electron-withdrawing, and halogen groups (including heteroaryl-substituted alkynylsilanes) provide hydroxymethylated products.
Synthesis and the crystal structure of dimeric 1-hydroxyhexane-2,3-dione and the spectral characteristics of a model acireductone
Trzewik, Bartosz,Chruszcz-Lipska, Katarzyna,Mi?aczewska, Anna,Opalińska-Piskorz, Joanna,Karcz, Robert,Grybo?, Robert,Oszajca, Marcin,Luberda-Durna?, Katarzyna,?asocha, Wies?aw,Fitch, Andy,Sulikowski, Bogdan,Borowski, Tomasz
supporting information, p. 9291 - 9303 (2016/11/11)
An efficient synthetic route to 1-hydroxyhexane-2,3-dione, which is a tautomeric form of a model acireductone, is presented here. Interestingly, the compound was found to crystallise as a stable dimer, a molecule of which contains a 1,3-dioxolane ring. The dimer structure was solved using the PXRD (powder X-ray diffraction) method and confirmed by NMR, IR, and Raman spectroscopy and DFT calculations. The title compound dissolves in water with the formation of several monomeric forms of the model acireductone as revealed by UV-Vis and NMR spectra. The extinction coefficients of the neutral and anionic forms of the monomer were also determined.
Copper(i) iodide catalyzed synthesis of primary propargylic alcohols from terminal alkyne
Kundu, Shrishnu Kumar,Mitra, Kanchan,Majee, Adinath
, p. 13220 - 13223 (2015/02/19)
A highly efficient and practical method for the synthesis of primary propargylic alcohols has been developed using CuI as catalyst and paraformaldehyde as the formaldehyde source. The reaction was performed under mild reaction conditions offering the desired products in good to excellent yields with a variety of terminal alkynes.
Substrate scope and stereocontrol in the Rh(II)-catalysed oxyamination of allylic carbamates
Unsworth, William P.,Lamont, Scott G.,Robertson, Jeremy
, p. 7388 - 7394 (2017/09/12)
Application of a modified Du Bois protocol for rhodium-stabilised nitrenoid generation to a variety of allylic carbamates results in 4-acetoxymethyl-1,3-oxazolidin-2-one derivatives with moderate to high levels of stereocontrol.
Tetris in monolayers: Patterned self-assembly using side chain shape
Xue, Yi,Zimmt, Matthew B.
supporting information; experimental part, p. 8832 - 8834 (2011/09/16)
The "kinked" shapes of conjugated alkadiynes constrain chain packing in monolayers on HOPG. Centrally located diyne units permit assembly of 1,5-bis(alkadiyne)anthracene monolayers. Off-center diynes inhibit self-assembly. Shape matched pairs of off-center diyne chains direct self-assembly of compositionally patterned, two component monolayers.
Au-catalyzed synthesis of 5,6-dihydro-8H-indolizin-7-ones from N-(pent-2-en-4-ynyl)-β-lactams
Peng, Yu,Yu, Meng,Zhang, Liming
supporting information; experimental part, p. 5187 - 5190 (2009/06/06)
(Chemical Equation Presented) Au-catalyzed synthesis of 5,6-dihydro-8H-indolizin-7-ones from readily available N-(pent-2-en-4-ynyl)- β-lactams is developed. In this reaction, a 5-exo-dig cyclization of the β-lactam nitrogen to the Au-activated C-C triple bond is followed by heterolytic fragmentation of the amide bond, forming a highly nucleophilic acyl cation. An expedient formal synthesis of indolizidine 167B was easily achieved using this new method.
Regio- and stereospecific formation of protected allylic alcohols via zirconium-mediated SN2′ substitution of allylic chlorides
Fox, Richard J.,Lalic, Gojko,Bergman, Robert G.
, p. 14144 - 14145 (2008/09/18)
A new, highly regio- and stereospecific SN2′ substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of E-allylic chlorides. A mechanism for the SN2′ allylic substitution consistent with kinetic, stereochemical, and secondary isotope effect studies was proposed. Copyright
