- Synthesis of sulfimides and N-Allyl-N-(thio)amides by Ru(II)catalyzed nitrene transfer reactions of N-acyloxyamides
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The N-acyloxyamides were employed as effective N-acyl nitrene precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies indicated that the Ru-nitrenoid species should be a key intermediate in the transformation.
- Zhang, Xinyu,Lin, Bo,Chen, Jianhui,Chen, Jiajia,Luo, Yanshu,Xia, Yuanzhi
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p. 819 - 825
(2021/02/01)
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- Stepwise Evolution of Fragment Hits against MAPK Interacting Kinases 1 and 2
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Dysregulation of translation initiation factor 4E (eIF4E) activity occurs in various cancers. Mitogen-activated protein kinase (MAPK) interacting kinases 1 and 2 (MNK1 and MNK2) play a fundamental role in activation of eIF4E. Structure-activity relationship-driven expansion of a fragment hit led to discovery of dual MNK1 and MNK2 inhibitors based on a novel pyridine-benzamide scaffold. The compounds possess promising in vitro and in vivo pharmacokinetic profiles and show potent on target inhibition of eIF4E phosphorylation in cells.
- Kwiatkowski, Jacek,Liu, Boping,Pang, Shermaine,Ahmad, Nur Huda Binte,Wang, Gang,Poulsen, Anders,Yang, Haiyan,Poh, Yong Rui,Tee, Doris Hui Ying,Ong, Esther,Retna, Priya,Dinie, Nurul,Kwek, Perlyn,Wee, John Liang Kuan,Manoharan, Vithya,Low, Choon Bing,Seah, Peck Gee,Pendharkar, Vishal,Sangthongpitag, Kanda,Joy, Joma,Baburajendran, Nithya,Jansson, Anna Elisabet,Nacro, Kassoum,Hill, Jeffrey,Keller, Thomas H.,Hung, Alvin W.
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p. 621 - 637
(2020/02/05)
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- Design and synthesis of dihydroisoquinolones for fragment-based drug discovery (FBDD)
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This study describes general synthesis aspects of fragments for FBDD, as illustrated by the dihydroisoquinolones 1-3. Previous Rh(iii) methodology is extended to incorporate amines, heteroatoms (N and S), and substituents (halogen, ester) as potential binding groups and/or synthetic growth points for fragment-to-lead elaboration.
- Palmer, Nick,Peakman, Torren M.,Norton, David,Rees, David C.
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p. 1599 - 1610
(2016/02/10)
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- Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent
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The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.
- Webb, Nicola J.,Marsden, Stephen P.,Raw, Steven A.
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supporting information
p. 4718 - 4721
(2015/04/27)
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- Rhodium-catalyzed C-H alkynylation of arenes at room temperature
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The rhodium(III)-catalyzed ortho C-H alkynylation of non-electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. Hot rhod: A rhodium-catalyzed, electronically reversed Sonogashira reaction between unbiased arenes and the hypervalent iodine reagent 1 proceeds through C-H activation. This reaction displays excellent functional-group tolerance and high efficiency, and thus opens a new synthetic pathway to access functionalized alkynes. Cp=C5Me5, DCE=1,2-dichloroethane, Piv=pivaloyl, TIPS=triisopropylsilyl.
- Feng, Chao,Loh, Teck-Peng
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p. 2722 - 2726
(2014/03/21)
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- Tunable arylative cyclization of 1,6-enynes triggered by rhodium(III)-catalyzed C-H activation
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Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an N-Michael addition process or hydrobenzofurans through a C-Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of CpRhIII-catalyzed C-H activation cascade reactions.
- Fukui, Yuki,Liu, Ping,Liu, Qiang,He, Zhi-Tao,Wu, Nuo-Yi,Tian, Ping,Lin, Guo-Qiang
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supporting information
p. 15607 - 15614
(2014/12/11)
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- Rh[III]-catalyzed direct C-H amination using N -chloroamines at room temperature
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An efficient Rh(III)-catalyzed direct C-H amination of N-pivaloyloxy benzamides with N-chloroamines proceeding at room temperature was achieved. The versatile directing group allows for selective mono- and diamination and can be readily converted to give valuable benzamide or aminoaniline derivatives. Mechanistic studies have been carried out to elucidate the reaction pathway.
- Grohmann, Christoph,Wang, Honggen,Glorius, Frank
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p. 656 - 659
(2012/03/08)
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- Mild rhodium(III)-catalyzed C-H activation and intermolecular annulation with allenes
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All(enes) great! A novel RhIII-catalyzed oxidative coupling with allenes under mild conditions provides heterocycles with exocyclic double bonds. This reaction features low catalyst loadings, high regio- and stereoselectivity, and excellent substrate scope. The products were derivatized and preliminary mechanistic studies were conducted. Copyright
- Wang, Honggen,Glorius, Frank
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p. 7318 - 7322
(2012/09/08)
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