74608-23-4Relevant articles and documents
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.
The Mechanism of Rhodium-Catalyzed Allylic C-H Amination
Harris, Robert J.,Park, Jiyong,Nelson, Taylor A. F.,Iqbal, Nafees,Salgueiro, Daniel C.,Bacsa, John,Macbeth, Cora E.,Baik, Mu-Hyun,Blakey, Simon B.
supporting information, p. 5842 - 5851 (2020/04/10)
Herein, the mechanism of catalytic allylic C-H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that the allylic C-H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidants in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry experiments concomitantly support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand proceeding through a Rh(IV) intermediate. Stoichiometric oxidation and bulk electrolysis of the proposed π-allyl intermediate are also reported to support these analyses. Lastly, evidence supporting the amination of an allylic acetate intermediate is presented. We show that Cp*Rh(III)2+ behaves as a Lewis acid catalyst to complete the allylic amination reaction.
Alkenyl Exchange of Allylamines via Nickel(0)-Catalyzed C-C Bond Cleavage
Fan, Chao,Lv, Xin-Yang,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
supporting information, p. 2889 - 2893 (2019/02/19)
A functional group exchange reaction between allylamines and alkenes via nickel-catalyzed C - C bond cleavage and formation was developed. This reaction provides a novel protocol, which does not require the use of unstable imine substrates, for the synthesis of allylamines, which are widely used in the production of fine chemicals, pharmaceuticals, and agrochemicals.
Arene Trifunctionalization with Highly Fused Ring Systems through a Domino Aryne Nucleophilic and Diels–Alder Cascade
He, Jia,Jia, Zizi,Tan, Hongcheng,Luo, Xiaohua,Qiu, Dachuan,Shi, Jiarong,Xu, Hai,Li, Yang
supporting information, p. 18513 - 18518 (2019/11/19)
A convenient and efficient domino aryne process was developed under transition-metal-free conditions to generate a range of tetra- and pentacyclic ring systems. This transformation was realized via a 1,2-benzdiyne through a nucleophilic and Diels–Alder reaction cascade using styrene as the diene moiety. Three new chemical bonds, namely one C?N and two C?C bonds, and two benzofused rings could be constructed concomitantly, which was made possible by distinct chemoselective control at both the 1,2-aryne and 2,3-aryne stages. Moreover, in-depth studies were carried out on the domino aryne precursors and controlling the diastereoselectivity.
Iron oxide-silver magnetic nanoparticles as simple heterogeneous catalysts for the direct inter/intramolecular nucleophilic substitution of π-activated alcohols with electron-deficient amines
Xu, Xingzhu,Wu, Haibo,Li, Zhengyi,Sun, Xiaoqiang,Wang, Zhiming
, p. 5254 - 5259 (2015/07/15)
The development of bimetallic iron oxide-silver magnetic nanoparticles (Fe2O3-Ag MNPs) catalytic system provides an efficient heterogeneous synthetic pathway to allylic amines and 1,2-dihydroquinolines involving the direct inter/intramolecular nucleophilic substitution of π-activated alcohols with electron-deficient amines. The major advantages of the present method are wide substrate scope, simple product separation, low catalyst loading, and magnetically recyclable catalyst.
Iron-catalyzed N-alkylation using π-activated ethers as electrophiles
Fan, Xiaohui,Fu, Lin-An,Li, Na,Lv, Hao,Cui, Xiao-Meng,Qi, Yuan
, p. 2147 - 2153 (2013/04/10)
A new method for the synthesis of diverse N-alkylation compounds was developed via an iron-catalyzed etheric Csp3-O cleavage with the C-N bond formation in the reaction of π-activated ethers with various nitrogen-based nucleophiles. In addition, the mechanism of this reaction was investigated. The Royal Society of Chemistry 2013.
Gold(I)-catalyzed stereoconvergent, intermolecular enantioselective hydroamination of allenes
Butler, Kristina L.,Tragni, Michele,Widenhoefer, Ross A.
supporting information; experimental part, p. 5175 - 5178 (2012/07/27)
Gold and silver: A 1:2 mixture of [{(S)-1}(AuCl)2] and AgBF 4 catalyzes the enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with N-unsubstituted carbamates to form N-allylic carbamates in good yield, with high regio- and diastereoselectivity, and up to 92% ee (see scheme, Cbz=benzyloxycarbonyl). Copyright
Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles
Trillo, Paz,Baeza, Alejandro,Najera, Carmen
, p. 7344 - 7354 (2012/10/30)
The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.
FeCl3·6H2O and TfOH as catalysts for allylic amination reaction: A comparative study
Trillo, Paz,Baeza, Alejandro,Najera, Carmen
scheme or table, 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
