- Aerobic Allylic Amination Catalyzed by a Pd(OAc)2/P(OPh)3System with Low Catalyst Loading
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A Pd(OAc)2/P(OPh)3 combination catalyzed Tsuji-Trost-Type allylic amination under aerobic conditions. Both aromatic and aliphatic secondary amines were transformed into the corresponding allylic amines with a tiny amount of the catalyst system (typically 0.02 mol % Pd), only when allylic phosphates were employed as electrophiles. Other typical electrophiles, such as allylic acetate and carbonate, were marginally reactive. A Pd(0) complex, Pd[P(OPh)3]3, formed in situ was suggested as an active species by mechanistic experiments.
- Ichihashi, Mizuki,Ohkuma, Takeshi,Saito, Sunaho,Yurino, Taiga
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- C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis
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Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O-i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize onto the nickel allyl intermediate prior to amination, generating carbocyclic amine products. This tandem process is only achieved under our cooperative catalytic system.
- Nazari, S. Hadi,Tiempos-Flores, Norma,Forson, Kelton G.,Bourdeau, Jefferson E.,Michaelis, David J.
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p. 10646 - 10654
(2018/09/06)
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- Practical regio- and stereoselective azidation and amination of terminal alkenes
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There is significant interest in developing more rapid and efficient production of nitrogen-containing allylic compounds, as widely used in various syntheses. This work reports a variety of allylic azides and allylic amines synthesized by an efficient, new one-pot protocol that employs readily available terminal alkenes as starting materials. This method is highly regio- and stereoselective, affording the linear (E)-isomer, under metal-free conditions. This process tolerates several functional groups including halogen-containing molecules; it is general for azides and amine nucleophiles; and, adducts were obtained in good yields.
- Ojo, Olatunji S.,Miranda, Octavio,Baumgardner, Kyle C.,Bugarin, Alejandro
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supporting information
p. 9354 - 9358
(2019/01/03)
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- Direct Allylic Amination of Allylic Alcohol Catalyzed by Palladium Complex Bearing Phosphine-Borane Ligand
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The direct electrophilic, nucleophilic, and amphiphilic allylations of allylic alcohol by use of a palladium catalyst and organometallic reagents such as organoborane and organozinc has been developed. The phosphine-borane compound works as the effective ligand for palladium-catalyzed direct allylic amination of allylic alcohol. Thus, with secondary amines, the reaction was completed in only 1 h, even at room temperature.
- Hirata, Goki,Satomura, Hideaki,Kumagae, Hidenobu,Shimizu, Aika,Onodera, Gen,Kimura, Masanari
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supporting information
p. 6148 - 6151
(2017/11/24)
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- Rhodium-Catalyzed Enantioselective Hydroamination of Alkynes with Indolines
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The hydroamination of internal alkynes via tandem rhodium catalysis gives branched N-allylic indolines with high regio- and enantioselectivity. An acid switch provides access to the linear isomer in preference to the branched isomer by an isomerization me
- Chen, Qing-An,Chen, Zhiwei,Dong, Vy M.
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supporting information
p. 8392 - 8395
(2015/07/15)
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- Photoredox α-vinylation of α-amino acids and N -aryl amines
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A new coupling protocol has been developed that allows the union of vinyl sulfones with photoredox-generated α-amino radicals to provide allylic amines of broad diversity. Direct C-H vinylations of N-aryl tertiary amines, as well as decarboxylative vinylations of N-Boc α-amino acids, proceed in high yield and with excellent olefin geometry control. The utility of this new allyl amine forming reaction has been demonstrated via the syntheses of several natural products and a number of established pharmacophores.
- Noble, Adam,MacMillan, David W. C.
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p. 11602 - 11605
(2014/11/08)
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- Deammoniative condensation of primary allylic amines with nonallylic amines
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An unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through C-N bond cleavage. In the presence of 5 mol% palladium diacetate, 10 mol% 1,4-bis(diphenylphosphino) butane (dppb), and 5 mol% p-toluenesulfonic acid (TsOH), a range of α-unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α-selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity. Replacing dppb with racemic 2,2-bis(diphenylphosphino)-1,1- binaphthyl (BINAP) permitted the deammoniative condensation of enantioenriched α-chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration. Electrospray ionization (ESI) mass spectrometric analysis of the reaction mixture permitted the identification of some π-allylpalladium intermediates, and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction. A range of enantioenriched primary allylic amines underwent palladium/acid-catalyzed direct substitution with nonallylic amines in a stereospecific manner. Copyright
- Wang, Yong,Li, Manbo,Ma, Xiantao,Liu, Congrong,Gu, Yonghong,Tian, Shi-Kai
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p. 741 - 751
(2014/10/15)
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- An efficient and convenient palladium catalyst system for the synthesis of amines from allylic alcohols
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A novel catalyst system for efficient amination of allylic alcohols with aryl and alkyl amines is presented. By applying a convenient combination consisting of Pd(OAc)2/1,10-phenanthroline, a variety of allylic alcohols reacted smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity. The usefulness of our protocol is demonstrated in the one-step synthesis of the antifungal drug naftifine and the calcium channel blocker flunarizine. One pot is all it takes: By applying a convenient combination consisting of Pd(OAc)2/1,10- phenanthroline, a variety of allylic alcohols reacts smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity (see picture).
- Banerjee, Debasis,Jagadeesh, Rajenahally V.,Junge, Kathrin,Junge, Henrik,Beller, Matthias
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p. 2039 - 2044
(2013/01/15)
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- Simple and convenient approach for synthesis of tetrahydroquinoline derivatives and studies on aza-Cope rearrangement
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A simple and novel synthesis of 1,2,3,4-tetrahydroquinoline derivatives by polyphosphoric acid-assisted reaction of N-aryl allyl anilines prepared from anilines has been reported. The generality and scope of the approach has been demonstrated by extending it to the synthesis of 1,2,5,6-tetrahydro-4H- pyrrolo[3,2,1-ij]quinoline (lilolidine) and 2,3,6,7-tetrahydro-1H,5H-pyrido[3,2, 1-ij]quinoline (julolidine). Further, Lewis acid- mediated aza-Cope rearrangement of various N-aryl allyl anilines has been demonstrated.
- Rao Lingam, V.S. Prasada,Thomas, Abraham,Mukkanti, Khagga,Gopalan, Balasubramanian
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experimental part
p. 1809 - 1828
(2011/06/20)
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- Surfactant-Enabled Transition Metal-Catalyzed Chemistry
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In one embodiment, the present application discloses mixtures comprising (a) water in an amount of at least 1% wt/wt of the mixture; (b) a transition metal catalyst; and (c) one or more solubilizing agents; and methods for using such mixtures for performing transition metal mediated bond formation reactions.
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- TPGS-750-M: A second-generation amphiphile for metal-catalyzed cross-couplings in water at room temperature
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An environmentally benign surfactant (TPGS-750-M), a diester composed of racemic α-tocopherol, MPEG-750, and succinic acid, has been designed and readily prepared as an effective nanomicelle-forming species for general use in metal-catalyzed cross-coupling reactions in water. Several "name" reactions, including Heck, Suzuki-Miyaura, Sonogashira, and Negishi-like couplings, have been studied using this technology, as have aminations, C-H activations, and olefin metathesis reactions. Physical data in the form of DLS and cryo-TEM measurements suggest that particle size and shape are key elements in achieving high levels of conversion and, hence, good isolated yields of products. This new amphiphile will soon be commercially available.
- Lipshutz, Bruce H.,Ghorai, Subir,Abela, Alexander R.,Moser, Ralph,Nishikata, Takashi,Duplais, Christophe,Krasovskiy, Arkady,Gaston, Ricky D.,Gadwood, Robert C.
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experimental part
p. 4379 - 4391
(2011/07/06)
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- Highly efficient and regioselective allylation with allylic alcohols catalyzed by [Mo3S4Pd(η3-allyl)] clusters
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(Figure presented) A highly efficient and regioselective allylation reaction of amines and active methylene compounds directly using allylic alcohols under mild conditions catalyzed by the novel cubane-type sulfido [(CpMo)3(μ3-S)4Pd(η3-allyl)] [PF6]2 clusters has been developed. A variety of allylic alcohols and nucleophiles including amines and active methylene compounds are investigated, and in the case of allylic alcohols bearing substituents at either the α- or γ-position only linear products are obtained.
- Tao, Yinsong,Wang, Bo,Wang, Baomin,Qu, Lihong,Qu, Jingping
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experimental part
p. 2726 - 2729
(2010/08/06)
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- Highly efficient and regioselective allylic amination of allylic alcohols catalyzed by [Mo3PdS4] cluster
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A highly efficient and regioselective allylation reaction of amines with allylic alcohols under mild conditions catalyzed by the cubane-type sulfido cluster [(Cp*Mo)3S4Pd(dba)][PF6] with H3BO3 as an additive has been developed. A variety of amines and allylic alcohols are investigated, and in the case of allylic alcohols bearing substituents at either α- or γ-position only linear allylic amination products are obtained.
- Tao, Yinsong,Zhou, Yuhan,Qu, Jingping,Hidai, Masanobu
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experimental part
p. 1982 - 1984
(2010/06/21)
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- Amination of allylic alcohols in water at room temperature
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The "trick" to carrying out regiocontrolled aminations of allylic alcohols in water as the only medium is use of a nanomicelle's interior as the organic reaction solvent. When HCO2Me is present, along with the proper base and source of catalytic Pd, allylic amines are cleanly formed at room temperature.
- Nishikata, Takashi,Lipshutz, Bruce H.
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supporting information; experimental part
p. 2377 - 2379
(2009/12/01)
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- Palladium nanoparticle-catalyzed C-N bond formation. A highly regio- and stereoselective allylic amination by allyl acetates
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(Chemical Equation Presented) Palladium nanoparticles, generated in situ from the reaction of palladium(II) chloride, have been demonstrated to be an efficient catalyst for C-N bond formation. A variety of aliphatic and aromatic amines have been allylated by substituted and unsubstituted allyl acetates in high yields by using palladium nanoparticles in the presence of a base without any ligand. The allylations are highly regio- and stereoselective.
- Adak, Laksmikanta,Chattopadhyay, Kalicharan,Ranu, Brindaban C.
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scheme or table
p. 3982 - 3985
(2009/10/17)
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- Highly chemoselective reductive amination of carbonyl compounds promoted by InCl3/Et3SiH/MeOH system
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(Chemical Equation Presented) A new strategy has been developed for reductive amination of aldehydes and ketones with the InCV Et 3SiH/MeOH system, which is a nontoxic system with highly chemoselective and nonwater sensitive properties. The methodology can be applied to a variety of cyclic, acyclic, aromatic, and aliphatic amines. Functionalities including ester, hydroxyl, carboxylic acid, and olefin are found to be stable under our conditions. The reaction shows a first-order kinetics profile with respect to both InCl3 and Et3SiH. Spectroscopic techniques such as NMR and ESI-MS have been employed to probe the active and resulting species arising from InCl3 and Et3SiH in MeOH, which are important in deriving a mechanistic proposal. In the ESI-MS studies, we have first discovered the existence of stable methanol-coordinated indium(III) species which are presumably responsible for the gentle generation of indium hydride at room temperature. The solvent attribution was crucial in tuning the reactivity of [In-H] species, leading to the establishment of mild reaction conditions. The system is superior in flexible tuning of hydride reactivity, resulting in the system being highly chemoselective.
- Lee, On-Yi,Law, Ka-Lun,Ho, Chun-Yu,Yang, Dan
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experimental part
p. 8829 - 8837
(2009/04/05)
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- Ruthenium-catalyzed linear selective allylic aminations of monosubstituted allyl acetates
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The ruthenium-catalyzed highly linear selective allylic amination of monosubstituted allylic acetates with secondary amines was developed. The regioselectivity was controlled by the Ru3(CO)12/2-DPPBA catalyst, and a linear-type aminated product was obtained as a single regioisomer.
- Kawatsura, Motoi,Ata, Fumio,Hirakawa, Takuya,Hayase, Shuichi,Itoh, Toshiyuki
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p. 4873 - 4875
(2008/09/21)
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- Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines
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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.
- Utsunomiya, Masaru,Miyamoto, Yoshiki,Lpposhi, Junji,Ohshima, Takashi,Mashima, Kazushi
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p. 3371 - 3374
(2008/02/12)
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- Palladium-catalyzed allylation of pronucleophiles with alkynes at 50°C - Remarkable effect of 2-(dicyclohexylphosphanyl)-2′-(dimethylamino) biphenyl as ligand
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The allylation of various pronucleophiles 1a-i with 1-phenylprop-1-yne (2) proceeded very smoothly at 50°C in the presence of catalytic amounts of Pd2(dba)3·CHCl3 (5 mol-%) and 2-(dicyclohexylphosphanyl)-2′-(dimethylamino)
- Patil, Nitin T.,Song, Dschun,Yamamoto, Yoshinori
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p. 4211 - 4213
(2007/10/03)
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- A convenient and efficient route for the allylation of aromatic amines and α-aryl aldehydes with alkynes in the presence of a Pd(0)TPhCOOH combined catalyst system
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The allylation of aromatic amines with alkynes proceeded smoothly in the presence of catalytic amounts of Pd(PPh3)4 and benzoic acid. The allylation products were obtained in high yields in a regio- and stereoselective manner. The effect of various groups on the nitrogen atom of anilines was studied. Regardless of the substituent (electron withdrawing or electron donating) on the aromatic ring, the reaction proceeded well. Various functionalities, including -CH3, -OMe, -Cl, -CN, -COOMe, -NO 2 and -COCH3 were tolerated under the reaction conditions. Similarly, the allylation of α-aryl aldehydes proceeded well with the same level of regio- and stereoselectivity as the allylation of aromatic amines. This reaction provides the second example of the transition metal catalyzed direct α-allylation of aldehydes.
- Patil, Nitin T.,Wu, Huanyou,Kadota, Isao,Yamamoto, Yoshinori
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p. 8745 - 8750
(2007/10/03)
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- Pd·Et3B-catalyzed alkylation of amines with allylic alcohols
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A combination of catalytic amounts of Pd (0.05 mmol) and Et3B (0.3 mmol) promotes allylic alkylation of primary and secondary aromatic and aliphatic amines (1.0 mmol) by the direct use of allylic alcohols, providing tertiary amines in excellent yields under mild conditions (room temperature ~ 50°C).
- Kimura, Masanari,Futamata, Makoto,Shibata, Kazufumi,Tamaru, Yoshinao
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p. 234 - 235
(2007/10/03)
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- REDUKTIVE METHYLIERUNG PRIMAERER UND SEKUNDAERER AMINE MIT HILFE VON FORMALDEHYD UND SALZEN DER PHOSPHORIGEN SAEURE
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Salts of phophorous acid were found to be useful alternative reducing agents for the reductive methylation of amines.
- Loibner, H.,Pruckner, A.,Stuetz, A.
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p. 2535 - 2536
(2007/10/02)
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