Search results for "Enol ether"
showing 10 items of 17 documents
Stereoselective synthesis of C-glycosyl compounds via Michael addition of trimethylsilyl enol ethers and enamines to hex-1-enopyran-3-uloses
1987
Abstract The titanium(IV)-catalyzed addition of trimethylsilyl enol ethers to 2,4,6-tri- O -acylhex - 1 - enopyran - 3 - uloses ( 3 and 4 ) gave stereoselectively 3,6 - di - O - acyl - 4 - deoxy - β - d - glycero -hex-3-enopyranosyl-2-ulose derivatives. The formation of the C -glycosyl bond was accompanied by a 2→3 acyl shift, followed by the elimination of the 4-acyloxy substituent. Similarly, the reaction of 1-pyrrolidinocyclohexene with 3 and 4 also led stereoselectively to 2-(2,4,6-tri- O -acyl-β- d - ribo -hexopyranosyl)cyclohexanones. In this Michael addition, among the eight possible diastereomers, only one was formed. The high stereocontrol of both C -glycosyl compound syntheses is …
Highly Enantioselective Protonation of the 3,4-Dihydro-2- methylnaphthalen-1(2H)-one Li-Enolate by TADDOLs
2000
A series of nine TADDOLs (=α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanols) 1a – 1i, have been tested as proton sources for the enantioselective protonation of the Li-enolate of 2-methyl-1-tetralone (=3,4-dihydro-2-methylnaphthalen-1(2H)-one). The enolate was generated directly from the ketone (with LiN(i-Pr)2 (LDA)/MeLi) or from the enol acetate (with 2 MeLi) or from the silyl enol ether (with MeLi) in CH2Cl2 or Et2O as the solvent (Scheme). The Li-enolate (associated with LiBr/LDA, or LiBr alone) was combined with 1.5 – 3.0 equiv. of the TADDOL at −78° by addition of the latter or by inverse addition. 2-Methyl-1-tetralone of (S)-configuration is formed (≤80% yield) with up to 99.5% sele…
Protonation and rearrangement of the tricyclo[4.2.2.22,5]dodeca-3,7,9,11-tetraene scaffold
2006
The biplanemers 2a,b contain enol ether substructures, which permit facile protonations of the π electron system. The subsequent ether cleavage is characterized by rearrangements of the polycyclic scaffold of the carbenium ions or the electroneutral primary products. Apart from the expected products 3a and 5a, a series of unexpected ketones and diketones (4a′, 9b, 10b, 11b, and 12b) were obtained.
Selective Synthesis of Z -Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones
2021
Journal of the American Chemical Society : JACS 143(22), 8375-8380 (2021). doi:10.1021/jacs.1c01797
Stereoselektive c-glycosidsynthese durch titan-(iv)-katalysierte addition von silylenolethern an 2-acyloxy-3-keto-glycale
1984
Abstract C-Glycosides are stereoselectively formed by the titan-(IV)-catalysed addition of silyl enolethers 2 to 2,4,6-tri-O-acyl-1-deoxy-D-erythro-hex-1-enopyran-3-uloses 1 followed by elimination of the 4-acyloxy substituent. Cyclohexenyl silylether 2a reacts with 2-acetoxy-3-keto-glycal derivative la forming only one product 3a . Thus, the reaction seems to be diastereospecific with respect to both new chiral centers of the product.
Stereoselective reactions of a thioester butanediacetal with various electrophiles
2014
Abstract The reactions of the lithium enolate of S -ethyl (2 R ,5 R ,6 R )-5,6-dimethoxy-5,6-dimethyl-[1,4]-dioxane-2-carbothioate were investigated in the presence or absence of hexamethylphosphoramide (HMPA). Fluorination gave a single isomer with a much better yield than for the corresponding methyl ester. Alkylation with alkyl halides strongly depended upon their structure. Without HMPA, only methyl iodide reacted with moderate yield and gave a single isomer. In the presence of HMPA, all of the alkyl halides reacted almost quantitatively (81–98% yield) with moderate stereoselectivity and preferentially gave products with the alkyl chain attached at the equatorial position. The silyl eno…
Vergleichende Untersuchung zur Diastereoselektivität derO-Methylierung von sterisch behinderten β-Ketocarbonsäureestern und ihren Enolen
1990
Diastereoselectivity of the O-Methylation of Sterically Hindered β-Ketocarboxylates and Their Enols The enols 1a, b, and 1c, which exists almost completely in the keto form, have been methylated at the oxygen atom with diazomethane. The regioselective reaction can be catalyzed by methanol, but may loose in that case the diastereoselectivity. A comparison with the methylation of the enolates by iodomethane is discussed.
Mukaiyama-type, eight-membered ring closure: Access to a tricyclic system related to taxanes
1998
Abstract Addition of Me2CuLi, with in situ trapping by TMSCl, to Hagemann's ester derivative 13, furnished silyl enol ether 14. Mukaiyama-type cyclization of the latter compound gave the tricyclic derivative 15, structurally related to the taxane core.
New acetylenes fromChrysanthemum coronarium L.
1990
The investigation of the aerial parts of Chrysanthemum coronarium yielded, in addition to several known compounds, two new acetylenic sulfoxides 9 and 10, and a new thiophene spiroacetal enol ether 11. Their structures were deduced by spectroscopic and chemical methods.
A DFT Study of the Domino Inter [4 + 2]/Intra [3 + 2] Cycloaddition Reactions of Nitroalkenes with Enol Ethers
2000
The molecular mechanism of the domino inter [4 + 2]/intra [3 + 2] cycloaddition reactions of nitroalkenes with enol ethers to give nitroso acetal adducts has been characterized using density functional theory methods with the B3LYP functional and the 6-31G* basis set. The presence of Lewis acid catalyst and solvent effects has been taken into account to model the experimental environment. These domino processes comprise two consecutive cycloaddition reactions: the first one is an intermolecular [4 + 2] cycloaddition of the enol ether to the nitroalkene to give a nitronate intermediate, which then affords the final nitroso acetal adduct through an intramolecular [3 + 2] cycloaddition reacti…