- Boron Lewis Acid Promoted Ruthenium-Catalyzed Hydrogenation of Amides: An Efficient Approach to Secondary Amines
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The hydrogenation of amides to amines has been developed by using the catalyst [Ru(H)2(CO)(Triphos)] (Triphos=1,1,1-tri(diphenylphosphinomethyl)ethane) and catalytic boron Lewis acids such as B(C6F5)3 or BF3?Et2O as additives. The reaction provides an efficient method for the preparation of secondary amines from amides in good yields with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhou, Qi-Lin
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- Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
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Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
- Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
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- Homogeneous cobalt-catalyzed deoxygenative hydrogenation of amides to amines
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The first general and efficient cobalt-catalyzed deoxygenative hydrogenation of amides to amines is presented. The optimal catalytic system based on a combination of [Co(NTf2)2] and (p-anisyl)triphos (L3) in the presence of [Me3SiOTf] as acidic co-catalyst facilitates the direct hydrogenation of a broad range of amides to the corresponding amines under mild conditions. A set of control experiments indicate that, after the initial reduction of the amide carboxylic group to the well-known hemiaminal intermediate, the reaction mainly proceeds through C-O bond cleavage though other pathways might be also involved to a minor extent. This journal is
- Papa, Veronica,Cabrero-Antonino, Jose R.,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
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p. 6116 - 6128
(2020/11/03)
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- Hydrogenation and: N-Alkylation of anilines and imines via transfer hydrogenation with homogeneous nickel compounds
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The nickel-catalyzed N-Alkylation of a variety of arylamines via transfer hydrogenation in the absence of pressurized hydrogen and basic or acidic additives was achieved in a tandem reaction. This process was further extended to the CN bond reduction and N-Alkylation of a variety of imines with ethanol, the latter acting as a hydrogen and acetaldehyde source, which allowed for the reduction and subsequent condensation to yield the corresponding N-Alkylated products.
- Benitez-Medina, G. Eliad,García, Juventino J.
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p. 17579 - 17587
(2019/12/23)
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- Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine
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A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Xu, Xin,Zhao, Haoqiang,Han, Jiahong,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
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supporting information
p. 3800 - 3806
(2019/07/12)
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- Deoxygenative Hydrogenation of Amides Catalyzed by a Well-Defined Iridium Pincer Complex
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The iridium-catalyzed highly chemoselective hydrogenation of amides to amines has been developed. Using a well-defined iridium catalyst bearing a P(O)C(O)P pincer ligand combined with B(C6F5)3, the C-O cleavage products are formed under mild reaction conditions. The reaction provides a new method for the preparation of amines from amides in good yield with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhu, Shou-Fei,Zhou, Qi-Lin
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p. 3665 - 3669
(2016/07/06)
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- Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines
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A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)3. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.
- Cabrero-Antonino, Jose R.,Alberico, Elisabetta,Junge, Kathrin,Junge, Henrik,Beller, Matthias
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p. 3432 - 3442
(2016/05/19)
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- Homogeneous catalytic hydrogenation of amides to amines
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Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4-pentanedione), triphos [1,1,1-tris- (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from prepared from [Ru(acac) 3], triphos and MSA, or from reactions of [RuX-(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crys-tallographically characterised complexes include: [Ru(OAc-κ1O) 2(H2O)-(triphos)], [Ru(OAc-κ2O,O') (CH3SO3-κ1O)(triphos)], [Ru(CH 3SO3-κ1O)2-(H 2O)(triphos)] and [Ru2(μ-CH3SO 3)3-(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc-κ1O)(OAc- κ2O,O')(triphos)],[Ru(CH3SO3- κ1O)(CH3SO3-κ2O,O')- (triphos)], H[Ru(CH3SO3-κ1O) 3-(triphos)], [RuH(CH3SO3-κ1O) (CO)-(triphos)] and [RuH(CH3SO3-k2O,O')- (triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed.
- Coetzee, Jacorien,Dodds, Deborah L.,Klankermayer, Jürgen,Brosinski, Sandra,Leitner, Walter,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
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supporting information
p. 11039 - 11050
(2013/09/02)
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- Assembly of substituted 2-alkylquinolines by a sequential palladium-catalyzed Ci-N and Ci-C bond formation
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Diversity: A range of substituted 2-alkylquinolines can be prepared in a general and efficient synthetic approach that employs mild reaction conditions (see scheme). The synthesis is based on a sequential palladium-catalyzed Ci-N and Ci-C bond formation, followed by palladium-catalyzed aromatization, and results in the formation of the desired compounds in one step. Copyright
- Matsubara, Yoshio,Hirakawa, Saori,Yamaguchi, Yoshihiro,Yoshida, Zen-Ichi
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experimental part
p. 7670 - 7673
(2011/10/05)
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- Pyrano-[2,3b]-pyridines as potassium channel antagonists
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The design and synthesis of a series of highly functionalized pyrano-[2,3b]-pyridines is described. These compounds were assayed for their ability to block the IKur channel encoded by the gene hKV1.5 in patch-clamped L-929 cells. Six of the compounds in this series showed sub-micromolar activity, the most potent being 4-(4-ethyl-benzenesulfonylamino)-3-hydroxy-2,2-dimethyl-3,4-dihydro-2H-pyrano[2,3b]-pyridine-6-carboxylic acid ethyl-phenyl-amide with an IC50 of 378 nM.
- Finlay, Heather J.,Lloyd, John,Nyman, Michael,Conder, Mary Lee,West, Tonya,Levesque, Paul,Atwal, Karnail
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p. 2714 - 2718
(2008/12/21)
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- Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles
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(Chemical Equation Presented) A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.
- Nacario, Ruel,Kotakonda, Shailaja,Fouchard, David M. D.,Tillekeratne, L. M. Viranga,Hudson, Richard A.
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p. 471 - 474
(2007/10/03)
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- One-pot reductive amination of acetals with aromatic amines using decaborane (B10H14) in methanol
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Aldehyde acetals and ketone ketals were reductively aminated in one pot with aromatic amines to give the corresponding amines in methanol or aqueous methanol in good to high yields. This direct method might be important because acetals and ketals are used as a popular protecting group for aldehyde and ketones. The advantage of our method is effective even in an aqueous solution and in the application to selective reaction.
- Park, Eun Soo,Lee, Ji Hee,Kim, Soo Jung,Yoon, Cheol Min
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p. 3387 - 3396
(2007/10/03)
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- Facile N-alkylation of anilines with alcohols over raney nickle under microwave irradiation
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The anilines could be easily and selectively N-alkylated with alcohols in the presence of a small amount of Raney nickel and with a greatly shortened period under microwave irradiation. A purely non-thermal effect of microwave was observed in the reaction.
- Jiang, Yu-Lin,Hu, Yu-Qiao,Feng, Shu-Qing,Wu, Ji-Shan,Wu, Zu-Wang,Yuan, Yun-Cheng,Liu, Jun-Min,Hao, Qing-Sheng,Li, De-Peng
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p. 161 - 164
(2007/10/03)
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- Bis(4-((chloro substituted phenyl)azo)anilino methylenes
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There are described novel yellow to red azo compounds of the formula I STR1 wherein each D independently of the other is the radical of an aromatic or heterocyclic diazo component, each Z independently of the other is hydrogen or a C1 -C4 -alkyl group or an acylamino group, Y is hydrogen or an unsubstituted or substituted C1 -C6 -alkyl group, X is either the direct bond or C1 -C6 -alkylene, STR2 and n is a number from 2 to 6, preferably 2; and the substituent Y, in the case of an unsubstituted or substituted C1 -C6 -alkyl group, can also be bonded to the o-position relative to the N atom of the phenylene group to form a six-membered ring, or both Y substituents can be linked together to form a C1 -C6 -alkylene bridge; described also are processes for producing the novel compounds, and their use as dyes for dyeing and printing natural and synthetic textile materials, particularly polyamide and wool materials, and also cotton, whereby there are obtained dyeings which are distinguished by good general fastness properties, especially by a good dye build-up, very good fastness to wet processing, good fastness to light, and good resistance to formaldehyde and good stability to hydrolysis.
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- Process for the preparation of aromatic secondary or tertiary amino compounds
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Aromatic secondary or tertiary amino compounds of the formula, STR1 wherein X is a hydrogen atom, a methyl group or a methoxygroup, and R is a C1 -C4 alkyl group, are produced by reacting hydrogen and an aromatic nitro compound of the formula, STR2 wherein X is as defined above, with an alcohol of the formula, wherein R is as defined above, in the presence of a catalyst of copper chromite.
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- Water-soluble acid azo dyestuff containing a N-(p-sulphophenoxyalkyl)-N-alkyl amino group
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STR1 wherein A is 2-thiazolyl, 4-nitro-2-thiazolyl, 2-benzothiazolyl, 6-methoxy-2-benzothiazolyl, 6-ethoxy-2-benzothiazolyl, 6-chloro-2-benzothiazolyl, 5,6-dichloro-2-benzothiazolyl, 4-bromo-6-chloro-2-benzothiazolyl, 4,6-dibromo-2-benzothiazolyl, 4-bromo-6-methoxy-2-benzothiazolyl, 4-bromo-6-ethoxy-2-benzothiazolyl, 4-bromo-5,6-dichloro-2-benzothiazolyl, 6-methylsulfonyl-2-benzothiazolyl, 4-bromo-6-methylsulfonyl-2-benzothiazolyl, or 6-hydroxyethylsulfonyl-2-benzothiazolyl, X is hydrogen, chlorine, methyl or trifluoromethyl, R is alkyl containing 1 to 4 carbon atoms, U is alkylene containing 1 to 5 carbon atoms, and y is hydrogen, chlorine or methyl. The dyestuffs are useful for the dyeing and printing of polyamide fibers for which they have a good affinity for polyamides so that the tinctorial yield is excellent and the exhaustion of the dyestuffs is very good. The colorations obtained have a remarkable brilliance, good fastness to washing and to light and finally good covering of bars i.e. absence of streakiness.
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