15645-60-0Relevant articles and documents
Structural Information from Tandem Mass Spectrometry for China White and Related Fentanyl Derivatives
Cheng, Michael T.,Kruppa, Gary H.,McLafferty, Fred W.,Cooper, Donald A.
, p. 2204 - 2207 (1982)
The potential of tandem mass spectrometry utilizing collisionally activated dissociation (CAD) for molecular structure determination is illustrated with α-methylfentanyl ("China White"), whose complex structure required several methods for its original el
Regio- and Enantioselective Iridium-Catalyzed Amination of Racemic Branched Alkyl-Substituted Allylic Acetates with Primary and Secondary Aromatic and Heteroaromatic Amines
Kim, Seung Wook,Schwartz, Leyah A.,Zbieg, Jason R.,Stivala, Craig E.,Krische, Michael J.
, p. 671 - 676 (2019)
The air- and water-stable π-allyliridium C,O-benzoate modified by (S)-tol-BINAP, (S)-Ir-II, catalyzes highly regio- and enantioselective Tsuji-Trost-type aminations of racemic branched alkyl-substituted allylic acetates using primary or secondary (hetero)aromatic amines. Specifically, in the presence of (S)-Ir-II (5 mol%) in DME solvent at 60-70 °C, α-methyl allyl acetate 1a (100 mol%) reacts with primary (hetero)aromatic amines 2a-2l (200 mol%) or secondary (hetero)aromatic amines 3a-3l (200 mol%) to form the branched products of allylic amination 4a-4l and 5a-5l, respectively, as single regioisomers in good to excellent yield with uniformly high levels of enantioselectivity. As illustrated by the conversion of heteroaromatic amine 3m to adducts 6a-6g, excellent levels of regio- and enantioselectivity are retained across diverse branched allylic acetates bearing normal alkyl or secondary alkyl substituents. For reactants 3n-3p, which incorporate both primary and secondary aryl amine moieties, regio- and enantioselective amination occurs with complete site-selectivity to furnish adducts 7a-7c. Mechanistic studies involving amination of the enantiomerically enriched, deuterium-labeled acetate 1h corroborate C-N bond formation via outer-sphere addition.
Palladium-catalyzed aerobic oxidative coupling of allylic alcohols with anilines in the synthesis of nitrogen heterocycles
Kumar, Gangam Srikanth,Singh, Diksha,Kumar, Manish,Kapur, Manmohan
supporting information, p. 3941 - 3951 (2018/04/14)
We report herein an unprecedented and expedient Pd-catalyzed oxidative coupling of allyl alcohols with anilines to afford β-amino ketones which are converted into substituted quinolines in a one-pot fashion. The exclusive preference for N-alkylation over N-allylation makes this approach unique when compared to those reported in literature. Detailed mechanistic investigations reveal that the conjugate addition pathway was the predominant one over the allylic amination pathway. The notable aspects of the present approach are the use of readily available, bench-stable allyl alcohols and molecular oxygen as the terminal oxidant, in the process dispensing the need for unstable and costly enones. Further, we explored the synthetic utility of β-amino ketones through an intramolecular α-arylation methodology and a one-pot domino annulation, thereby providing rapid access to indolines and quinolines.
Cooperative catalysis by palladium and a chiral phosphoric acid: Enantioselective amination of racemic allylic alcohols
Banerjee, Debasis,Junge, Kathrin,Beller, Matthias
supporting information, p. 13049 - 13053 (2015/01/16)
Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This
Hydrogen-bond-assisted activation of allylic alcohols for palladium-catalyzed coupling reactions
Gumrukcu, Yasemin,Debruin, Bas,Reek, Joost N. H.
, p. 890 - 896 (2014/03/21)
We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive. Hydrogen Bond Rule(s): Direct activation of allylic alcohols and subsequent alkylation and amination reactions are reported. The new catalyst is based on functionalized palladium and phosphoramidite ligands to allow hydrogen bond-assisted activation. Kinetic data are in line with this mechanism as the oxidative addition is the rate-determining step.
Platinum-catalyzed direct amination of allylic alcohols under mild conditions: Ligand and microwave effects, substrate scope, and mechanistic study
Ohshima, Takashi,Miyamoto, Yoshiki,Ipposhi, Junji,Nakahara, Yasuhito,Utsunomiya, Masaru,Mashima, Kazushi
supporting information; body text, p. 14317 - 14328 (2010/02/16)
Transition metal-catalyzed amination of allylic compounds via a π-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including 1H and 31P{1H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl2, Pt(η2-C3H5OH)(xantphos), etc; confirmation of the structure of [Pt(η3-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the π-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.
Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines
Utsunomiya, Masaru,Miyamoto, Yoshiki,Lpposhi, Junji,Ohshima, Takashi,Mashima, Kazushi
, p. 3371 - 3374 (2008/02/12)
A new direct catalytic amination of allylic alcohols promoted by the combination of platinum and a large bite-angle ligand DPEphos was developed in which the allylic alcohol was effectively converted to a π-allylplatinum intermediate without the use of an activating reagent. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of a variety of monoallylation products in good to excellent yield.
Regioselective iron-catalyzed allylic amination
Plietker, Bernd
, p. 6053 - 6056 (2007/10/03)
(Chemical Equation Presented) Iron age: An air- and water-resistant iron(-II) catalyst, in the presence of triphenylphosphane under buffered conditions, allows for the highly regioselective and stereoselective allylation of primary aromatic amines. A broa
Synthesis of secondary amines by titanium-mediated transfer of alkenyl groups from alcohols
Ramanathan, Balasubramanian,Odom, Aaron L.
, p. 9344 - 9345 (2007/10/03)
Reaction of Ti(NMe2)4 with allyl alcohols and primary amines leads to the selective formation of secondary allylic amines. The allyl transfer from the alcohol to the amine occurs with selective allylic transposition. Due to substituent effects in the reactions, we postulate that the reaction occurs through a [2 + 2]/retro-[2 + 2]-cycloaddition mechanism. It was also found that a similar reaction could be accomplished with homoallylic alcohol. In this case, the more complex mechanism leads to the formation of 1-aza-spiro[5.5]undecane. Possible pathways for the homoallylic transfer and cyclization are discussed. Copyright
Direct palladium/carboxylic acid-catalyzed allylation of anilines with allylic alcohols in water
Yang, Shyh-Chyun,Hsu, Yi-Chun,Gan, Kim-Hong
, p. 3949 - 3958 (2007/10/03)
The direct activation of C-O bonds in allylic alcohols in water as a suspension medium by palladium complexes has been accelerated by carrying out the reactions in the presence of a carboxylic acid. The palladium-catalyzed allylation of anilines using allylic alcohols directly gave allylic anilines in good yields.
