- Retraction: Harnessing Thiol as a Benzyl Reagent for Photocatalytic Reductive Benzylation of Imines (Organic Letters DOI: 10.1021/2Facs.orglett.0c00065)
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The authors retract this article after finding in subsequent studies that the quality of the purchased catalysts has a notable impact on the reproducibility of the results. Accordingly, the authors note that additional work is necessary to understand the
- Zhang, Jinghui,Zhang, Muliang
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- Addition of benzyltrimethylsilane to imines triggered by tetrabutylammonium fluoride
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The addition of benzyltrimethylsilane 2 to imines 1 triggered by TBAF in the presence of 4A molecular sieves gave rise to the corresponding α-benzylated amines 3 in good yields. Moderate to high diastereoselectivity was obtained in the reactions of tert-b
- Zhang, Wan-Xuan,Ding, Chang-Hua,Luo, Zhi-Bin,Hou, Xue-Long,Dai, Li-Xin
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- Secondary amine compound synthesized from alkyne and synthesis method of secondary amine compound
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The invention relates to a secondary amine compound synthesized from alkyne and a synthesis method of the secondary amine compound. The specific structure of the compound is shown as the formula II inthe description. Meanwhile, the invention discloses the three-step one-pot synthesis method of the compound. According to the method, cheap and available acetenyl substituted benzene (I) is taken asa raw material. The method comprises steps as follows: step 1), fluorine-containing alcohol and water are taken as solvents and subjected to a hydration reaction under catalysis of trifluoromethanesulfonic acid, and an intermediate ketone is generated; step 2), aromatic amines are added directly to a reaction system, and imine is generated; step 3), tetrahydroxydiboron is added to the system, anda product II is obtained. No metal participates in the method, operation is simple and convenient, the raw materials are easily available, reaction conditions are mild, and yield is relatively high.
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- Radical alkylation of imines with 4-alkyl-1,4-dihydropyridines enabled by photoredox/br?nsted acid cocatalysis
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Radical alkylation of imines with 4-alkyl-1,4-dihydropyridines cocatalyzed by iridium/ruthenium complex and Br?nsted acid under visible light irradiation has been achieved. Both aldimines and ketimines can undergo this transformation. Common functional groups, such as hydroxyl groups, ester, amide, ether, cyanide, and heterocycles, can be tolerated in this reaction. A variety of structurally diverse amines (57 examples) have been produced with up to 98% isolated yields using this method.
- Zhang, Hong-Hao,Yu, Shouyun
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supporting information
p. 9995 - 10006
(2018/05/31)
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- Palladium-catalyzed benzylic C-H benzylation via bis-benzylpalladium(II) complexes in water: An effective pathway for the direct construction of N-(1,2-diphenylethyl)anilines
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A strategy for the N-benzylation/benzylic C-H benzylation cascade of anilines by the π-benzylpalladium system using a water-soluble palladium(0)/sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) catalyst and benzyl alcohol in water has been developed. This tandem process is devised as a novel and efficient synthetic route for N-(1,2-diphenylethyl)anilines. Benzylic C-H activation of a mono-N-benzylated intermediate with a π-benzylpalladium(II) complex affords a bis-π-benzylated palladium(II) intermediate. The nucleophilic η1-σ-benzyl anion ligand attacks the electrophilic η3-π-benzyl ligand to give a dibenzylated product. The intermolecular competition between mono-N-benzylaniline and its monodeuterated form (monodeuterated at the benzylic group) with benzyl alcohol gave a KIE=4.6, suggesting that C-H bond cleavage was involved in the rate-determining step. Hammett studies on the rate constants of benzylation by various substituted anthranilic acids and mono-N-benzylanilines show a good correlation between the log(kX/kH) and the σ values of the respective substituents. From the slope, negative ρ values are obtained, suggesting that there is a build-up of positive charge in the transition state. The reaction of anilines with electron-donating and electron-withdrawing groups affords the corresponding N-(1,2-diphenylethyl)anilines in moderate to good yields (54-86%). Interestingly, the reaction of anthranilic acids proceeded smoothly to give only the corresponding dibenzylated products in good to excellent yields (70-87%). The carboxyl group of the anthranilic acids acts as a directing group in the benzylic C-H activation process.
- Hikawa, Hidemasa,Izumi, Kyoko,Ino, Yukari,Kikkawa, Shoko,Yokoyama, Yuusaku,Azumaya, Isao
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p. 1037 - 1048
(2015/03/30)
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- Bis(amidate)bis(amido) titanium complex: A regioselective intermolecular alkyne hydroamination catalyst
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An efficient and selective bis(amidate)bis(amido) titanium precatalyst for the anti-Markovnikov hydroamination of alkynes is reported. Hydroamination of terminal and internal alkynes with primary alkylamines, arylamines, and hydrazines is promoted by 5-10 mol % of Ti catalyst. Various functional groups are tolerated including esters, protected alcohols, and imines. The in situ generated complex shows comparable catalytic activity, demonstrating its synthetic versatility for benchtop application. Applications of this catalyst for the synthesis of amino alcohols and a one-pot procedure for indole synthesis are described. A mechanistic proposal that invokes turnover-limiting protonolysis is presented to rationalize the observed regioselectivities.
- Yim, Jacky C.-H.,Bexrud, Jason A.,Ayinla, Rashidat O.,Leitch, David C.,Schafer, Laurel L.
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p. 2015 - 2028
(2014/04/03)
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- Highly enantioselective hydrosilylation of N-(1,2-diarylethylidene) arylamines
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By employing a chiral Lewis base as the catalyst, enantioselective hydrosilylation of N-(1,2-diarylethylidene)arylamines was realized. The reactions proceeded smoothly to afford various chiral 1,2-diarylethanamines with good yields (up to 99%) in good ena
- Zheng, Yongsheng,Xue, Zhouyang,Liu, Lixin,Shu, Chang,Yuan, Weicheng,Zhang, Xiaomei
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supporting information
p. 412 - 415
(2013/02/23)
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- Copper acetoacetonate [Cu(acac)2]/BINAP-promoted Csp 3-N bond formation via reductive coupling of N-tosylhydrazones with anilines
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We report the the copper(II) acetoacetonate [Cu(acac)2]/BINAP- catalyzed synthesis of arylamines from N-tosylhydrazones and anilines. A fine tuning of the reaction conditions was required to accomplish the cross-coupling successfully, including the ligands effect and the addition of small amounts of water. The characteristic feature of this protocol is its functional group compatibility and its chemoselectivity when various aminophenol derivatives were used. Taking into consideration the interest for this copper-reductive coupling in which no stoichiometric metal hydride reagent is employed, this can be considered as an alternative to the conventional reductive amination.
- Aziz, Jessy,Brion, Jean-Daniel,Hamze, Abdallah,Alami, Mouad
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p. 2417 - 2429
(2013/10/01)
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- Alkyl transfer from C-C cleavage
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Hydrogenation was only the beginning: Hantzsch esters have now been used to transfer alkyl groups to imines under mild catalytic conditions to provide a variety of amines (see scheme). Benzyl, secondary alkyl, and tertiary alkyl groups containing ether, ester, and hydroxy functionalities were transferred successfully. The use of Hantzsch esters as alkylation reagents offers a practical and complementary alternative to organometallic processes. Copyright
- Li, Guangxun,Chen, Rong,Wu, Lei,Fu, Qingquan,Zhang, Xiaomei,Tang, Zhuo
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supporting information
p. 8432 - 8436
(2013/09/02)
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- Tetrabenzylhafnium as a new organometallic reagent for imine addition resulting in α-branched amines
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Tetrabenzylhafnium has been explored as a new organometallic reagent for the imine addition reaction. This reagent tolerates a wide scope of imines, affording α-branched amines in excellent yields without the use of any additive or catalyst. This new reag
- Mei, Haibo,Ji, Xiaoyun,Han, Jianlin,Pan, Yi
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supporting information; experimental part
p. 5783 - 5786
(2011/11/06)
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- BNAH-mediated free radical addition to aromatic imines
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Benzyl radical is added regioselectively to the carbon-nitrogen double bond of aromatic imines by UV irradiation (λ > 300 nm) of a ternary mixture of benzyl bromide/aromatic imines/1-benzyl-1,4-dihydronicotinamide (BNAH) in acetonitrile via a BNAH-mediated photoinduced electron transfer mechanism. (C) 2000 Elsevier Science Ltd.
- Jin,Zhang,Yang,Liu,Liu
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p. 7357 - 7360
(2007/10/03)
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