- Asymmetric Synthesis of Fluorinated Allenes by Rhodium-Catalyzed Enantioselective Alkylation/Defluorination of Propargyl Difluorides with Alkylzincs
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The reaction of propargyl difluorides R1CF2C≡CR2 with alkylzincs R3ZnCl giving axially chiral fluorinated allenes R1FC=C=CR2R3 with high enantioselectivity (up to 99 % ee) was found to be catalyzed by a chiral diene/rhodium complex. A key step in the catalytic cycle is selective elimination of one of the enantiotopic fluorides at the β-position of an alkenyl-Rh intermediate, which is generated by regioselective addition of R3-Rh onto the triple bond of the starting difluorides.
- Hayashi, Tamio,Ng, Jia Sheng
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supporting information
p. 20771 - 20775
(2021/08/25)
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- TRIAZOLOQUINAZOLINONE SYNTHESIS
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The invention relates to an improved process for preparing triazoloquinazolinones of Formula (I), including 9-benzyl-2-(4-methylphenyl)-2,6-dihydro[l,2,4]triazolo[4,3-c]quinazoline-3,5-dione, pharmaceutical compositions comprising the compounds of Formula (I), including 9-benzyl-2-(4- methylphenyl)-2,6-dihydro[l,2,4]triazolo[4,3-c]quinazoline-3,5-dione, prepared by the improved process, and methods of treatment using the compounds of Formula (I), including 9-benzyl-2-(4- methylphenyl)-2,6-dihydro[l,2,4]triazolo[4,3-c]quinazoline-3,5-dione, prepared by the improved process.
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Paragraph 041; 049; 050; 051
(2019/07/13)
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- Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer
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Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.
- Keaveney, Sinead T.,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 12573 - 12577
(2018/09/18)
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- Mechanochemical Activation of Zinc and Application to Negishi Cross-Coupling
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A form independent activation of zinc, concomitant generation of organozinc species and engagement in a Negishi cross-coupling reaction via mechanochemical methods is reported. The reported method exhibits a broad substrate scope for both C(sp3)–C(sp2) and C(sp2)–C(sp2) couplings and is tolerant to many important functional groups. The method may offer broad reaching opportunities for the in situ generation organometallic compounds from base metals and their concomitant engagement in synthetic reactions via mechanochemical methods.
- Cao, Qun,Howard, Joseph L.,Wheatley, Emilie,Browne, Duncan L.
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supporting information
p. 11339 - 11343
(2018/08/28)
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- Straightforward Synthesis of 2- and 2,8-Substituted Tetracenes
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A simple regiospecific route to otherwise problematic substituted tetracenes is described. The diverse cores (E)-1,2-Ar1CH2(HOCH2)C=C(CH2OH)I (Ar1=Ph, 4-MePh, 4-MeOPh, 4-FPh) and (E)-1,2-I(HOCH2)C=C(CH2OH)I, accessed from ultra-low cost HOCH2C≡CCH2OH at multi-gram scales, allow the synthesis of diol libraries (E)-1,2-Ar1CH2(HOCH2)C=C(CH2OH)CH2Ar2 (Ar2=Ph, 4-MePh, 4-iPrPh, 4-MeOPh, 4-FPh, 4-BrPh, 4-biphenyl, 4-styryl; 14 examples) by efficient Negishi coupling. Copper-catalysed aerobic oxidation cleanly provides dialdehydes (E)-1,2-Ar1CH2(CHO)C=C(CHO)CH2Ar2, which in many cases undergo titanium(IV) chloride-induced double Bradsher closure, providing a convenient method for the synthesis of regiochemically and analytically pure tetracenes (12 examples). The sequence is typically chromatography-free, scalable, efficient and technically simple to carry out.
- Woodward, Simon,Ackermann, Miriam,Ahirwar, Saurabh K.,Burroughs, Laurence,Garrett, Mary Robert,Ritchie, John,Shine, Jonathan,Tyril, Bj?rk,Simpson, Kevin,Woodward, Peter
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supporting information
p. 7819 - 7824
(2017/06/06)
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- A practical cobalt-catalyzed cross-coupling of benzylic zinc reagents with aryl and heteroaryl bromides or chlorides
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A catalytic system consisting of 5 mol% CoCl2 and 10 mol% isoquinoline allows a convenient cross-coupling of benzylic zinc reagents with various aryl and heteroaryl bromides or chlorides leading to polyfunctionalized diaryl- and aryl-heteroaryl-methane derivatives.
- Benischke, Andreas D.,Knoll, Irina,Rérat, Alice,Gosmini, Corinne,Knochel, Paul
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supporting information
p. 3171 - 3174
(2016/02/20)
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- CuI catalyzed sulfonylation of organozinc reagents with sulfonyl halides
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In this study, a facile CuI catalyzed synthesis of sulfones involving a nucleophilic addition of functionalized organozinc reagents to organic sulfonyl chlorides is realized. This reaction proceeds efficiently at room temperature, giving rise to various functional group substituted sulfones, generally in moderate to high yields. The method provides a novel, simple, and promising strategy for functionalized sulfone synthesis in the research field of sulfur chemistry. the Partner Organisations 2014.
- Fu, Ying,Zhu, Wenbo,Zhao, Xingling,Huegel, Helmut,Wu, Zhouqiang,Su, Yuhu,Du, Zhengyin,Huang, Danfeng,Hu, Yulai
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supporting information
p. 4295 - 4299
(2014/06/23)
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- Nickel-catalyzed C-F bond activation and alkylation of polyfluoroaryl imines
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In this paper we show the C-F bond activation and alkylation in polyfluoroaryl imines. An active trimethylphosphine supported nickel-catalyzed cross-coupling reaction of polyfluoroaryl imines with ZnMe2 under mild conditions is described. According to the in situ 19F NMR spectroscopic data, the substrates are quantitatively converted into di-methylation products, while mono-methylation can also be realized under the controlled conditions in moderate yields. Apart from ZnMe2, other organozinc regents were tried in this system. However, due to the nucleophilicity and steric hindrance, they show much lower reactivity than ZnMe2. Only in the case of benzylic zinc chloride, the dibenzylation product can be obtained quantitatively by raising temperature to 90 °C. The results reported here will benefit the development of C-F bond activation as well as the diversity of Schiff bases.
- Yang, Xiuxiu,Sun, Hongjian,Zhang, Shumiao,Li, Xiaoyan
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- Polyfunctional benzylic zinc chlorides by the direct insertion of magnesium into benzylic chlorides in the presence of LiCl and ZnCl2
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Benzylic zinc chlorides bearing various functional groups are smoothly prepared by the direct insertion of magnesium into benzylic chlorides in the presence of LiCl and ZnCl2. The Royal Society of Chemistry.
- Metzger, Albrecht,Piller, Fabian M.,Knochel, Paul
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p. 5824 - 5826
(2009/04/13)
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- SIX-MEMBERED HETEROCYCLES USEFUL AS SERINE PROTEASE INHIBITORS
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The present invention provides compounds of Formula (I), or a stereoisomer, tautomer, pharmaceutically acceptable salt or solvate form thereof, wherein the variables A, B, R3 and R11 are as defined herein. The compounds of Formula (I) are useful as selective inhibitors of serine protease enzymes of the coagulation cascade and/or contact activation system; for example thrombin, factor Xa, factor XIa, factor IXa, factor VIIa and/or plasma kallikrein. In particular, it relates to compounds that are selective factor XIa inhibitors or dual inhibitors of fXIa and plasma kallikrein. This invention also relates to pharmaceutical compositions comprising these compounds and methods of treating thromboembolic and/or inflammatory disorders using the same.
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Page/Page column 97
(2008/06/13)
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