1024757-02-5Relevant academic research and scientific papers
Gold versus silver-catalyzed amination of allylic alcohols
Giner, Xavier,Trillo, Paz,Nájera, Carmen
, p. 357 - 361 (2011)
Direct substitution of the hydroxy group in allylic alcohols by different nitrogenated nucleophiles is performed using low loadings of cationic gold(I) or silver salts as catalysts. Sulfonamides, carbamates and aromatic amines can be used as nucleophiles. Comparative studies between the best catalysts, cationic (triphenylphosphite)gold(I) complex and silver triflate, demonstrate that the former catalyst shows, in general, better performance than silver, working at lower loadings, in shorter reaction times and at lower temperatures. Representative allylic alcohols are used giving good γ-regioselectivity, specially in the case of penta-1,4-dien-3-ol and (E)-1-phenylbut-2-en-1-ol affording the corresponding allylic sulfonamides with total regio and stereoselectivity by a hydroamination mechanism. In the case of crotyl alcohol and (E)-4-phenylbut-3-en-2-ol mainly and exclusively α-substituted sulfonamides were obtained, respectively, by a cationic mechanism.
Rh(iii)-Catalyzed allylic C-H amidation of unactivated alkenes within situgenerated iminoiodinanes
Jeganmohan, Masilamani,Sihag, Pinki
supporting information, p. 6428 - 6431 (2021/07/02)
Rh(iii)-catalyzed allylic C-H amidation of substituted alkenes within situgenerated iminoiodinanes is demonstrated. The presented protocol is compatible with differently functionalized unactivated terminal alkenes and internal alkenes. In terminal alkenes
H-*BEA Zeolite-Catalyzed Nucleophilic Substitution in Allyl Alcohols Using Sulfonamides, Amides, and Anilines
Aoki, Shunsuke,Fujii, Takeshi,Morita, Sachiko,Nishida, Ryo,Ohtsuki, Akimichi,Okumura, Kazu
, (2020/07/24)
Herein, we report a novel zeolite-catalyzed nucleophilic substitution in allyl alcohols. The product yield was improved upon the addition of NaOTf (0.05 mol-percent) using the studied zeolites. The highest yields were observed using H-*BEA(Si/Al2 = 40)/NaOTf. The scope of the reaction with respect to the nucleophile was examined using 1,3-diphenylprop-2-ene-1-ol as a model substrate under optimized reaction conditions. p-Substituted aryl sulfonamides bearing electron-rich or electron-deficient substituents, alkyl sulfonamides, and heteroaryl sulfonamides undergo the amidation reaction to produce their corresponding allyl sulfonamides in good yield. Amides and anilines exhibited low activity under the optimized conditions, however, performing the reaction at 90 °C produced the target product. The scope of the allyl alcohol was investigated using p-toluenesulfonamide as the nucleophile and the reaction proceeded with a variety of allylic alcohols. To probe the practical utility of the H-*BEA-catalyzed amidation reaction, a gram-scale reaction was performed using 1.01 g (4.8 mmol) of allyl alcohol, which afforded the target product in 88 percent yield.
Iridium(III)-Catalyzed Intermolecular Allylic C-H Amidation of Internal Alkenes with Sulfonamides
Sihag, Pinki,Jeganmohan, Masilamani
, p. 13053 - 13064 (2019/10/02)
The Ir(III)-catalyzed direct allylic C-H amidation of substituted internal alkenes with substituted sulfonamides without having directing group is demonstrated. The present protocol provides substituted allylic amines in a highly atom- and step-economical
Direct substitution of hydroxy group of π-activated alcohols with electron-deficient amines using Re2O7 catalyst
Das, Braja Gopal,Nallagonda, Rajender,Ghorai, Prasanta
experimental part, p. 5577 - 5583 (2012/07/31)
The first example of simple Re2O7-catalyzed direct dehydrative coupling between allylic alcohols with electron-deficient amines has been achieved under mild and open flask conditions. The protocol has also been successfully applied t
Mild and efficient allylation of indoles and amides using Amberlyst-15 as a recyclable heterogeneous catalyst
Liu, Zhe,Wang, Dong,Wu, Yanchao,Chen, Yongjun
experimental part, p. 1813 - 1823 (2012/04/10)
A mild and efficient allylation of indoles and amides in the presence of a catalytic amount of Amberlyst-15 has been described in this context. The recyclable heterogeneous catalytic system is practical and facile for the synthesis of C- and N-allylated d
FeCl3·6H2O and TfOH as catalysts for allylic amination reaction: A comparative study
Trillo, Paz,Baeza, Alejandro,Najera, Carmen
experimental part, p. 2929 - 2934 (2012/06/29)
The use of FeCl3·6H2O and TfOH as readily available and easy-to-handle catalysts for the direct allylic amination reaction using a wide variety of nitrogenated nucleophiles onto different free allylic alcohols is described. Comparative studies between these catalysts, as representative Lewis and Bronsted acids are conducted, concluding that both are suitable catalysts for this transformation. The reactions are performed in a flask open to air and using technical grade 1,4-dioxane. In light of the results obtained from this study it can be asserted that TfOH turned out to be slightly superior than the FeIII salt since similar or better yields are obtained in most of the cases using lower catalyst loadings and milder reaction conditions. A similar trend is observed when carbonucleophiles were employed in the allylic substitution reaction. Studies for the elucidation of the reaction mechanism are in agreement with a carbocationic intermediate, being the regioselectivity governed by the stability of the final product. Copyright
Mild and efficient iodine-catalyzed direct substitution of hydroxy group of alcohols with c- and n-nucleophiles
Liu, Zhe,Wang, Dong,Chen, Yongjun
experimental part, p. 73 - 80 (2012/04/23)
A mild and efficient iodine-catalyzed direct substitution of hydroxy group of allylic, progargylic and other alcohols with various C- and N-nucleophiles was described in this contribution. C-C and C-N bond formations could be readily achieved by non-metal
A homogeneous, recyclable polymer support for rh(I)-catalyzed c-c bond formation
Jana, Ranjan,Tunge, Jon A.
experimental part, p. 8376 - 8385 (2011/12/04)
A robust and practical polymer-supported, homogeneous, recyclable biphephos rhodium(I) catalyst has been developed for C-C bond formation reactions. Control of polymer molecular weight allowed tuning of the polymer solubility such that the polymer-supported catalyst is soluble in nonpolar solvents and insoluble in polar solvents. Using the supported rhodium catalysts, addition of aryl and vinylboronic acids to the electrophiles such as enones, aldehydes, N-sulfonyl aldimines, and alkynes occurs smoothly to provide products in high yields. Additions of terminal alkynes to enones and industrially relevant hydroformylation reactions have also been successfully carried out. Studies show that the leaching of Rh from the polymer support is low and catalyst recycle can be achieved by simple precipitation and filtration.
Rhodium-catalyzed addition of organo[2-(hydroxymethyl)phenyl] dimethylsilanes to arenesulfonylimines
Nakao, Yoshiaki,Takeda, Masahide,Chen, Jinshui,Hiyama, Tamejiro,Ichikawa, Yoshitaka,Shintani, Ryo,Hayashi, Tamio
, p. 290 - 291 (2008/09/20)
The title reaction is found to proceed in the presence of a rhodium/diene catalyst. Variously substituted diarylmethylamines and allylamines having an N-arenesulfonyl protection are obtained in good yields, which are important building blocks in organic synthesis. Copyright
