81256-39-5Relevant academic research and scientific papers
Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy
Yang, Peng,Wang, Xiuhua,Ma, Yu,Sun, Yaxin,Zhang, Li,Yue, Jieyu,Fu, Kaiyue,Zhou, Jianrong Steve,Tang, Bo
supporting information, p. 14083 - 14086 (2020/11/20)
A simple catalyst of Ni(OAc)2 and P(t-Bu)3 enables selective C-alkylation of thioacetamides and primary acetamides with alcohols for the first time. Monoalkylation of thioamides, amides and t-butyl esters occurs in excellent yields (>95%). Mechanistic studies reveal that the reaction proceeds via a hydrogen autotransfer pathway. This journal is
Generation of alkyl radicals from alkylsilyl peroxides and their applications to C-N or C-O bond formations
Sakurai, Shunya,Kato, Terumasa,Sakamoto, Ryu,Maruoka, Keiji
, p. 172 - 179 (2018/12/11)
This article describes a novel method for the generation of alkyl radicals from alkylsilyl peroxides and their applications to the Cu-catalyzed mono-N-alkylation of amides or arylamines, and to the O-alkylation of carboxylic acids. The use of alkylsilyl peroxides as alkyl radical sources includes the following synthetic advantages: i) various alkylsilyl peroxides can be readily synthesized from the corresponding alcohols and be stored at bench, and ii) a variety of alkyl radicals can be generated efficiently under mild conditions.
The cubane paradigm in bioactive molecule discovery: Further scope, limitations and the cyclooctatetraene complement
Houston, Sevan D.,Fahrenhorst-Jones, Tyler,Xing, Hui,Chalmers, Benjamin A.,Sykes, Melissa L.,Stok, Jeanette E.,Farfan Soto, Clementina,Burns, Jed M.,Bernhardt, Paul V.,De Voss, James J.,Boyle, Glen M.,Smith, Maree T.,Tsanaktsidis, John,Savage, G. Paul,Avery, Vicky M.,Williams, Craig M.
supporting information, p. 6790 - 6798 (2019/07/22)
The cubane phenyl ring bioisostere paradigm was further explored in an extensive study covering a wide range of pharmaceutical and agrochemical templates, which included antibiotics (cefaclor, penicillin G) and antihistamine (diphenhydramine), a smooth muscle relaxant (alverine), an anaesthetic (ketamine), an agrochemical instecticide (triflumuron), an antiparasitic (benznidazole) and an anticancer agent (tamibarotene). This investigation highlights the scope and limitations of incorporating cubane into bioactive molecule discovery, both in terms of synthetic compatibility and physical property matching. Cubane maintained bioisosterism in the case of the Chagas disease antiparasitic benznidazole, although it was less active in the case of the anticancer agent (tamibarotenne). Application of the cyclooctatetraene (COT) (bio)motif complement was found to optimize benznidazole relative to the benzene parent, and augmented anticancer activity relative to the cubane analogue in the case of tamibarotene. Like all bioisosteres, scaffolds and biomotifs, however, there are limitations (e.g. synthetic implementation), and these have been specifically highlighted herein using failed examples. A summary of all templates prepared to date by our group that were biologically evaluated strongly supports the concept that cubane is a valuable tool in bioactive molecule discovery and COT is a viable complement.
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.
A highly efficient catalytic α-alkylation of unactivated amides using primary alcohols
Yao, Wubing,Ma, Xiaochen,Guo, Le,Jia, Xiangqing,Hu, Aiguo,Huang, Zheng
supporting information, p. 2919 - 2921 (2016/06/13)
The α-alkylation of unactivated amides with alcohols is described. Using a NCP-type pincer Ir complex as the precatalyst and KOtBu as the base, the reactions of secondary or tertiary acetamides with benzyl or nonbenzyl primary alcohols occur at 80 °C, furnishing the alkylation products in good yields. This method represents a practical and green means of α-alkylation of amides in a relatively mild, efficient, and selective manner with low catalyst loadings (0.5 mol %).
Palladium on graphene: The in situ generation of a catalyst for the chemoselective reduction of α,β-unsaturated carbonyl compounds
Morimoto, Naoki,Yamamoto, Shun-Ichi,Takeuchi, Yasuo,Nishina, Yuta
, p. 15608 - 15612 (2013/09/12)
Palladium-supported graphene oxide has been successfully applied as a catalyst precursor for the selective reduction of α,β-unsaturated carbonyl compounds. Pd nanoparticles were formed during the course of the reduction with only negligible leaching of the Pd species into the reaction mixture.
Iridium-catalyzed selective α-alkylation of unactivated amides with primary alcohols
Guo, Le,Liu, Yinghua,Yao, Wubing,Leng, Xuebing,Huang, Zheng
supporting information, p. 1144 - 1147 (2013/04/10)
The first α-alkylation of unactivated amides with primary alcohols is described. An effective and robust iridium pincer complex has been developed for selective α-alkylation of tertiary and secondary acetamides involving a borrowing hydrogen methodology. The method is compatible with alcohols bearing various functional groups. This presents a convenient and environmentally benign protocol for α-alkylation of amides.
Practical access to amines by platinum-catalyzed reduction of carboxamides with hydrosilanes: Synergy of dual Si-H groups leads to high efficiency and selectivity
Hanada, Shiori,Tsutsumi, Emi,Motoyama, Yukihiro,Nagashima, Hideo
supporting information; experimental part, p. 15032 - 15040 (2010/01/29)
The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions. The rate of the reaction is dependent on the distance of two Si-H groups; 1,1,3,3-tetramethyldisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO2, CO2R, CN, CdC, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
A versatile, practical, and inexpensive reagent, pyridine-3-carboxylic anhydride (3-PCA), for condensation reactions
Funasaka, Setsuo,Mukaiyama, Teruaki
experimental part, p. 148 - 159 (2009/04/06)
A highly useful method for the preparation of carboxylic esters and carboxamides from various carboxylic acids was established by using a novel condensing reagent, pyridine-3-carboxylic anhydride (3-PCA), in the presence of 4-(dimethylamino)pyridine as an activator. The reactions of various carboxylic acids with nucleophiles, such as alcohols or amines, afforded the corresponding carboxylic acids or carboxamides in good to high yields under mild conditions by using simple experimental procedure. In addition, it was confirmed that this protocol was applicable to a gram-scale synthesis and the by-products, including pyridine-3-carboxylic acid and pyridine-3-carboxylate (or pyridine-3- carboxamide) produced in situ, were easily removed by using a simple aqueous workup.
