- Synthesis of Non-Terminal Alkenyl Ethers, Alkenyl Sulfides, and N-Vinylazoles from Arylaldehydes or Diarylketones, DMSO and O, S, N-Nucleophiles
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A transition-metal-free protocol for the synthesis of non-terminal alkenyl ethers, alkenyl sulfides, and N-vinylazoles from arylaldehydes or diarylketones, DMSO and O, S, N-nucleophiles has been reported. In this protocol, 24 examples of non-terminal alkenyl ethers and 28 examples of non-terminal alkenyl sulfides in 72–95% yields have been synthesized within 5 min. Moreover, 27 examples of non-terminal N-vinylazoles with 57–88% yields have also been synthesized within 2 hours. The preliminary mechanism investigations revealed that arylaldehydes or diarylketones offered a carbon atom, DMSO provided a methine and O, S, N-nucleophiles contributed one X atom for constructing C=C?X structure. (Figure presented.).
- Nie, Zhiwen,Lv, Huifang,Yang, Tonglin,Su, Miaodong,Luo, Weiping,Liu, Qiang,Guo, Cancheng
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supporting information
p. 1473 - 1480
(2022/04/03)
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- [3+1+1+1] Annulation to the Pyridine Structure in Quinoline Molecules Based on DMSO as a Nonadjacent Dual-Methine Synthon: Simple Synthesis of 3-Arylquinolines from Arylaldehydes, Arylamines, and DMSO
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A [3+1+1+1] annulation of arylamines, arylaldehydes, and dimethyl sulfoxide (DMSO) to the pyridine structure in quinolines using DMSO as a nonadjacent dual-methine (═CH?) synthon is disclosed. In this annulation, arylamines provide two carbon atoms and one nitrogen atom, arylaldehydes furnish one carbon atom, and DMSO provides two nonadjacent methines (═CH?) to the pyridine ring in quinoline molecules. This annulation provides a simple approach for the synthesis of 3-arylquinolines from readily available substrates in useful yields. On the basis of the control experiments and the literature, a plausible mechanism is proposed.
- Guo, Can-Cheng,Li, Hui,Liu, Qiang,Luo, Wei-Ping,Nie, Zhiwen,Su, Miao-Dong,Yang, Tonglin
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- Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines
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An unexpected annulation among 2-aminobenzyl alcohols, benzaldehydes, and DMSO to quinolines has been disclosed. For the reported annulation between 2-aminobenzyl alcohols and benzaldehydes, the change of the solvent from toluene to DMSO led to the change of the product from the diheteroatomic cyclic benzoxazines to monoheteroatomic cyclic quinolines. This annulation can be used to synthesize regioselectively different substituted quinolines by the choice of different 2-amino alcohols, aldehydes, and sulfoxides as substrates. Interestingly, introducing substituent groups to the α-position of sulfoxides resulted in the interchange of the positions between benzaldehydes and sulfoxides in the product quinolines. On the basis of the control experiments and literatures, a plausible mechanism for this annulation was proposed.
- Yang, Tonglin,Nie, Zhi-Wen,Su, Miao-Dong,Li, Hui,Luo, Wei-Ping,Liu, Qiang,Guo, Can-Cheng
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p. 15228 - 15241
(2021/10/25)
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- Synthesis of Terminal N-Vinylazoles from Aromatic Aldehydes, DMSO, and Azoles Based DMSO as Terminal Carbon Synthon
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A protocol for the synthesis of terminal N-vinylazoles from aromatic aldehydes, DMSO, and azoles has been reported. In this strategy, DMSO was involved in the construction of the C=C bond as a terminal carbon synthon. Both aromatic aldehydes and azoles could be well tolerated and give the corresponding terminal N-vinylazoles in 52–91% yields. Based on preliminary experiments, a plausible mechanism is proposed. (Figure presented.).
- Nie, Zhiwen,Lv, Huifang,Li, Hui,Su, Miaodong,Yang, Tonglin,Luo, Weiping,Liu, Qiang,Guo, Cancheng
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p. 4621 - 4626
(2021/09/02)
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- Base-promoted formal [4?+?1+1] annulation of aldehyde, N-benzyl amidine and DMSO toward 2,4,6-triaryl pyrimidines
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A base-promoted formal [4 + 1+1] annulation of aldehyde, N-benzyl amidine and DMSO was developed, leading to a series of 2,4,6-triaryl pyrimidines in moderate to good yields. Notably, DMSO served as a methine source, which was activated by base rather than either Lewis acid or electrophile. Molecular O2 was the sole eco-friendly oxidant during this procedure.
- Yuan, Jin,Li, Jingbo,Wang, Bingbing,Sun, Song,Cheng, Jiang
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supporting information
p. 4783 - 4785
(2017/12/01)
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- Styryl ether formation from benzyl alcohols under transition-metal-free basic DMSO conditions
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A phenol-catalyzed aerobic oxidative styryl ether formation method was developed with benzyl alcohol under basic DMSO. Styryl ether was obtained after 12 hours of heating at 60-80 °C where DMSO was involved in the reaction as the extra carbon source. Control experiments indicated that both phenol and DMSO are crucial for the success of the reaction. A variety of styryl ethers were prepared smoothly from benzyl alcohols in good to excellent yields in an environmentally friendly way. This journal is
- Yang, Kai,Song, Qiuling
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p. 2267 - 2272
(2015/03/04)
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- Direct syntheses of styryl ethers from benzyl alcohols via ag nanoparticle-catalyzed tandem aerobic oxidation
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Ag nanoparticle-catalyzed aerobic oxidation of benzyl alcohols in basic DMSO gave efficient formation of styryl ethers, featuring single carbon transfer and Ci - C and C-O bond formation. A deuterium labeling experiment established that DMSO was the carbo
- Zhang, Qi,Cai, Shuangfei,Li, Linsen,Chen, Yifeng,Rong, Hongpan,Niu, Zhiqiang,Liu, Junjia,He, Wei,Li, Yadong
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p. 1681 - 1684
(2013/07/26)
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- Synthesis of (±)-7-hydroxylycopodine
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A seven-step synthesis of (±)-7-hydroxylycopodine that proceeds in 5% overall yield has been achieved. The key step is a Prins reaction in 60% sulfuric acid that gave the key tricyclic intermediate with complete control of the ring fusion stereochemistry. A one-pot procedure orthogonally protected the primary alcohol as an acetate and the tertiary alcohol as a methylthiomethyl ether. The resulting product was converted to 7-hydroxydehydrolycopodine by heating with KO-t-Bu and benzophenone in benzene followed by acidic workup. During unsuccessful attempts to make optically pure starting material, we observed the selective Pt-catalyzed hydrogenation of the 5-phenyl group of a 4,5-diphenyloxazolidine under acidic conditions and the Pt-catalyzed isomerization of the oxazolidine to an amide under neutral conditions. In attempts to hydroxylate the starting material so that we could adapt this synthesis to the preparation of (±)-7,8-dihydroxylycopodine (sauroine) we observed the novel oxidation of a bicyclic vinylogous amide to a keto pyridine with Mn(OAc)3 and to an amino phenol with KHMDS and oxygen.
- Lin, Hong-Yu,Causey, Robert,Garcia, Gregory E.,Snider, Barry B.
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p. 7143 - 7156
(2012/11/06)
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- Convenient one-step synthesis of cis-2,4,5-triarylimidazolines from aromatic aldehydes with urea
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A simple and efficient method has been developed for the synthesis of cis-2,4,5-triarylimidazolines based on a one-step procedure of aldehydes and urea in the presence of cesium carbonate. Taylor & Francis Group, LLC.
- Wang, Fei,Liao, Qian,Xi, Chanjuan
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experimental part
p. 905 - 913
(2012/02/01)
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- Stereoselective synthesis of (E)-Vinyl Sulfoxides by the Horner-Wittig reaction
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The Horner-Wittig reaction of sulfinylmethyl-substituted di-phenylphosphane oxides 1-3 with aldehydes is reported. In a straightforward synthesis, (E)-vinyl sulfoxides 4 (R1 = Ph), 5 (R1 = Me) and 6 (R1=pTol) were formed m
- Van Steenis, Jan Hein,Van Es, Joseph Johannes Gerardus Steven,Van Der Gen, Arne
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p. 2787 - 2793
(2007/10/03)
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- Stereoselective synthesis of racemic and optically active E-vinyl and E- dienyl sulfoxides via Wittig reaction of α-sulfinyl phosphonium ylides
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A series of α-sulfinyl phosphonium ylides have been obtained in the reaction of phosphonium mono- and diylides with sulfinic acid esters. The use of (-)-(S)-menthyl p-toluenesulfinate in this reaction afforded the corresponding (S)-((p-tolylsulfinyl)methyl)triphenylphosphonium ylide. The Wittig reaction of these ylides with saturated and unsaturated aldehydes resulted in the formation of racemic and optically active (+)-(R)-vinyl and dienyl sulfoxides with the E-geometry. The synthesis of (+)-(R)-((p- tolylsulfinyl)methyl)triphenylphosphonium iodide as a precursor of the optically active ylide has also been described.
- Mikolajczyk, Marian,Perlikowska, Wieslawa,Omelanczuk, Jan,Cristau, Henri-Jean,Perraud-Darcy, Anne
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p. 9716 - 9722
(2007/10/03)
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- Theoretical and experimental analyses of the deprotonation of thiirane S-oxides: The stereoselective formation of trans-alkyl- and gem-silylethenesulfenate anions
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Experimental and theoretical studies of the regioselective deprotonation of thiirane S-oxides are reported. Experimentally under the reaction conditions of LiHMDS/THF/-78°C with anti-alkylthiirane S-oxides or anti-silylthiirane S-oxides as starting materials, the products of ring-opening are (E)-2-alkylethenesulfenate and 1-silylethenesulfenate anions, respectively. Experiments involving deuterium labeling clearly indicate that a regioselective deprotonation reaction was followed by a stereoselective ring-opening. Ab initio methods at both the Hartree-Fock and M?ller-Plesset perturbation theory levels with the 6-31+G(d) basis set were used to examine both lithiated methyl- and silylthiirane S-oxides. Of the possible anti-substituted species, the coordination of the lithium anti to the methyl and gem to the silyl is predicted to be the most stable. These stable intermediates with the lithium syn to the sulfoxide could ring-open to yield the experimentally observed products.
- Refvik, Mitchell D.,Froese, Robert D. J.,Goddard, John D.,Pham, Hung H.,Pippert, Mark F.,Schwan, Adrian L.
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p. 184 - 192
(2007/10/02)
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- On the conformational preferences of the dehydrochlorination of α-chlorosulfoxides
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Several acyclic α-chlorosulfoxides have been shown to undergo a γ-dehydrochlorination upon treatment with LDA.The proposed immediate products of γ-dehydrochlorination, thiirane-S-oxides, are unstable under the basic conditions and react further with the LDA; the isolated products are usually E-alkenes and (or) E-vinyl sulfoxides.Some of the proposed intermediate thiirane-S-oxides, compounds 6, 7, 8, and 18, were synthesized independently and treated with one equivalent of LDA in order to mimic the second step of the overall dehydrochlorination/ring opening sequence.The products obtained from the reactions of compounds 6 and 18 compared favourably with those products which were believed to arise from certain conformations of α-chlorosulfoxides 1kB and 1e, respectively.Tha addition of one equivalent of LDA to 1kA afforded a mixture containing thiirane-S-oxide 8, which is proposed as the immediate product of γ-dehydrochlorination of 1kA.The configurations of 1kB and 1hA were both shown to be threo by X-ray crystallographic studies.Those conformations which are preferred for the dehydrochlorination possess a geometry where the sulfinyl oxygen is anti to any of the substituents of the ring carbons.
- Schwan, Adrian L.,Roche, Michael R.,Gallagher, John F.,Ferguson, George
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p. 312 - 324
(2007/10/02)
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- The One-pot Generation and Ring Opening of Alkyl and Aryl Thiirane-S-oxides
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Base induced dehydrochlorination of acyclic α-chlorosulfoxides affords thiirane-S-oxides which react further under the alkaline reaction conditions.
- Schwan, Adrian L.,Wilson, David A.
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p. 5897 - 5900
(2007/10/02)
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- REACTIONS OF EPISULPHOXIDES AND EPISULPHIDES WITH ORGANOLITHIUM REAGENTS
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Reactions of aryl-substituted episulphoxides and episulphides with butyl- and phenyllithium, lithium di-isopropyl amide and lithium dimethylcuprate have been examined.The following reaction paths could be observed: a) attack at sulphur leading to olefins with complete retention of configuration at the carbon skeleton; b) attack at proton leading to a vinyl sulphenate in the case of episulphoxides, or to a thiolate anion, in the case of episulphides, trapped as methyl vinyl sulphoxide or methyl vinyl sulphide, respectively; c) attack at carbon, observed only in thereaction of styrene episulphoxide with lithium dimethylcuprate, leading to a saturated sulphenate anion trapped as alkyl methyl sulphoxide.Mechanisms and stereochemistry of these processes are discussed.
- Bonini, Bianca F.,Maccagnani, Gaetano,Mazzanti, Germana,Zani, Paolo
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p. 115 - 121
(2007/10/02)
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- An Uncomplicated Synthesis of α-Styrylenol Ethers and Arylacetaldehydes from Benzyl Alcohols
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The reaction of benzyl alcohol with potassium hydroxide in dimethyl sulfoxide yielding (E)-β-(benzyloxy)styrene is described.The mechanism proposed for this reaction was studied by isotope labelling and by introduction of probable intermediates.The reacti
- Langhals, Heinz,Julia, Marc,Uguen, Daniel
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p. 2216 - 2222
(2007/10/02)
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