27845-85-8Relevant academic research and scientific papers
Redox-Neutral Photocatalytic Cyclopropanation via Radical/Polar Crossover
Phelan, James P.,Lang, Simon B.,Compton, Jordan S.,Kelly, Christopher B.,Dykstra, Ryan,Gutierrez, Osvaldo,Molander, Gary A.
supporting information, p. 8037 - 8047 (2018/07/03)
A benchtop stable, bifunctional reagent for the redox-neutral cyclopropanation of olefins has been developed. Triethylammonium bis(catecholato)iodomethylsilicate can be readily prepared on multigram scale. Using this reagent in combination with an organic photocatalyst and visible light, cyclopropanation of an array of olefins, including trifluoromethyl- and pinacolatoboryl-substituted alkenes, can be accomplished in a matter of hours. The reaction is highly tolerant of traditionally reactive functional groups (carboxylic acids, basic heterocycles, alkyl halides, etc.) and permits the chemoselective cyclopropanation of polyolefinated compounds. Mechanistic interrogation revealed that the reaction proceeds via a rapid anionic 3-exo-tet ring closure, a pathway consistent with experimental and computational data.
Bioactivity and structure–activity relationship of cinnamic acid derivatives and its heteroaromatic ring analogues as potential high-efficient acaricides against Psoroptes cuniculi
Chen, Dong-Dong,Zhang, Bing-Yu,Liu, Xiu-Xiu,Li, Xing-Qiang,Yang, Xin-Juan,Zhou, Le
supporting information, p. 1149 - 1153 (2018/03/05)
A series of cinnamic acid derivatives and its heteroaromatic ring analogues were synthesized and evaluated for acaricidal activity in vitro against Psoroptes cuniculi, a mange mite. Among them, eight compounds showed the higher activity with median lethal concentrations (LC50) of 0.36–1.07 mM (60.4–192.1 μg/mL) and great potential for the development of novel acaricidal agent. Compound 40 showed both the lowest LC50 value of 0.36 mM (60.4 μg/mL) and the smallest median lethal time (LT50) of 2.6 h at 4.5 mM, comparable with ivermectin [LC50 = 0.28 mM (247.4 μg/mL), LT50 = 8.9 h], an acaricidal drug standard. SAR analysis showed that the carbonyl group is crucial for the activity. The type and chain length of the alkoxy in the ester moiety and the steric hindrance near the ester group significantly influence the activity. The esters were more active than the corresponding thiol esters, amides, ketones or acids. Replacement of the phenyl group of cinnamic esters with α-pyridyl or α-furanyl significantly increase the activity. Thus, a series of cinnamic esters and its heteroaromatic ring analogues with excellent acaricidal activity emerged.
Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-: N -alkylation of primary amides
Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
supporting information, p. 6484 - 6487 (2017/07/10)
The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.
Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines
Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
supporting information, p. 9030 - 9033 (2017/07/11)
The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides.
Highly efficient diastereoselective exo Diels-Alder reactions of homochiral 2-(N-acylamino)-1-thia-1,3-dienes: A powerful entry into optically pure thiopyrans
Bell, Andrew S.,Fishwick, Colin W.G.,Reed, Jessica E.
, p. 123 - 126 (2007/10/02)
4-Phenyl-2-N-(R-(-)-α-(2-naphthyl)ethylamino)-1-thia-1,3-dienes when activated by acetyl chloride, undergo extremely efficient diastereoselective exo Diels-Alder cycloadditions giving access to thiopyrans of high optical purity.
Reactions of N-Cinnamoylaziridines by Generation of Aziridino Ketyls from Homolytic Cleavage of Michael Adducts
Bentz, Gunther,Werry, Juergen,Stamm, Helmut
, p. 2793 - 2798 (2007/10/02)
High yields of the pyrrolidinones 2a, b are obtained from N-cinnamoylaziridines 1a, b and the carbanion 'anthracene hydride' (anion of dihydroanthracene).Aziridino ketyls 3a, b are intermediates that probably arise by way of base-initiated homolytic fragm
HOMOLYTIC AZIRIDINE OPENING (AZA VARIANT OF CYCLOPROPYLCARBINYL-HOMOALLYL REARRANGEMENT) BY ADDITION OF TRIBUTYLTIN RADICAL TO N-ACYLAZIRIDINES. FACTORS CONTRIBUTING TO THE REGIOSELECTIVITY
Werry, Juergen,Stamm, Helmut,Lin, Pen-Yuan,Falkenstein, Reinhard,Gries, Stefan,Irngartinger, Hermann
, p. 5015 - 5028 (2007/10/02)
AIBN initiated reaction of N-acylaziridines 1 with Bu3SnH in refluxing benzene provided products 5 and 8 of reductive ring opening.Yields (practically quantitative in most cases) fell drastically with steric hindrance of the addition of Bu3Sn to the acyl oxygen of 1.They depended to some extent on the experimental conditions for hydrogen capturing when aziridine homolysis provided a primary radical 3 or 6.The regioselectivity of (probably reversible) ring homolysis can be understood in terms of the stability of the arising radical (3, 6), of stereoelectronic control (e.g. 1i as compared to 1h) and of frontier orbital interactions (1j).A possible difference in bond lengths as explanation for the formation of the primary radical from 1j did not find support from an X-ray structure analysis of N-tosyl-2-methyl-aziridine 11.Isomeric products were obtained only twice (1i, 1j) with a dependence of the ratio 5j:8j on concentration and hydrogen isotope of Bu3SnH.No such dependence was found for the ratio 5:14 (reduction without and with an intervening cyclization of 3 leading to a pyrrolidone) obtained from the N-cinnamoylaziridine 1l.This ratio (1:9 for 1l and 1:3 for 1n) must reflect the E-Z isomers in 3.The observed preference for the formation of E-3 from 2 can be explained by stereoelectronic and steric effects.A cinnamoyl double bond in 5 was saturated depending on experimental conditions.
