24279-06-9Relevant articles and documents
Corrigendum to: Ligand-Controlled Regiodivergent Pathways of Rhodium(III)-Catalyzed Dihydroisoquinolone Synthesis: Experimental and Computational Studies of Different Cyclopentadienyl Ligands (Chemistry - A European Journal, (2014), 20, 47, (15409-15418), 10.1002/chem.201404515)
Wodrich, Matthew D.,Ye, Baihua,Gonthier, Jér?me F.,Corminboeuf, Clémence,Cramer, Nicolai
supporting information, p. 7727 - 7727 (2020/06/16)
The authors became aware that product 4aa was erroneously assigned to 4-phenyl- 3,4-dihydroisoquinolin-1(2H)-one. Reanalysis of the 1H NMR and 13C NMR spectra of product 4aa confirmed that the correct structure corresponds to the constitutional 3-benzyl-isoindolones isomer (Figure 1). 4-Phenyl-3,4-dihydroisoquinolin-1(2H)-one was reported by Ellman and its structure was confirmed by X-ray crystallographic analysis.[1] The corrected isoindolone structure of 4aa matches all data of 3-benzylisoindolone synthesized by a different route.[2]. (Figure presented.).
Ligand-Controlled Regiodivergent Pathways of Rhodium(III)-Catalyzed Dihydroisoquinolone Synthesis: Experimental and Computational Studies of Different Cyclopentadienyl Ligands
Wodrich, Matthew D.,Ye, Baihua,Gonthier, Jér?me F.,Corminboeuf, Clémence,Cramer, Nicolai
supporting information, p. 15409 - 15418 (2016/02/18)
RhIII-catalyzed directed C-H functionalizations of arylhydroxamates have become a valuable synthetic tool. To date, the regioselectivity of the insertion of the unsaturated acceptor into the common cyclometalated intermediate was dependent solely on intrinsic substrate control. Herein, we report two different catalytic systems that allow the selective formation of regioisomeric 3-aryl dihydroisoquinolones and previously inaccessible 4-aryl dihydroisoquinolones under full catalyst control. The differences in the catalysts are computationally examined using density functional theory and transition state theory of different possible pathways to elucidate key contributing factors leading to the regioisomeric products. The stabilities of the initially formed rhodium complex styrene adducts, as well as activation barrier differences for the migratory insertion, were identified as key contributing factors for the regiodivergent pathways. RhIII-catalyzed directed C-H functionalization of aryl hydroxamates enables the selective formation of regioisomeric 3-aryl or 4-aryl dihydroisoquinolones with two different catalytic systems. The different selectivities are examined using DFT and transition state theory. The stabilities of the rhodium complex adducts and migratory-insertion activation barriers are key factors for the regiodivergent pathways (see scheme; rs=regioselectivity).
Easy access to (n+3)-dimethylamino-1-ethenylbicyclo[n.1.0]alkanes and their facile conversion to ring-annelated cyclopentadienes
Voigt, Tobias,Winsel, Harald,De Meijere, Armin
, p. 1362 - 1364 (2007/10/03)
Aminocyclopropanation of 1-ethenylcycloalkenes 2a-d with N,N-dibenzyl- and N,N-dimethylformamide, respectively, by treatment with cyclohexylmagnesium bromide in the presence of methyltitanium triisopropoxide yielded the exo-(n+3)-N,N-dimethylamino-1-ethenylbicyclo[n.1.0]alkanes 3a-d (58-72%). Compounds 7b-d could be transformed by thermal vinylcyclopropane to cyclopentene rearrangement to the corresponding exo-4-dimethylaminobicyclo[n.3.0]alk-1-enes 7b-d (84-90%). Elimination of the dimethylamino group led to the cyclopentadienes 11b-d and 121b-d (72-82%). The 5-dimethylamino-1-ethenylbicyclo[2.1.0]pentane did not undergo the typical vinylcyclopropane rearrangement, but ring-opening at the bridgehead-bridgehead bond to form 1-ethenyl-2-dimethylaminocyclopentene 8.
Synthesis and properties of novel substituted 4,5,6,7-tetrahydroindenes and selected metal complexes
Austin, Rachel N.,Clark, T. Jeffrey,Dickson, Thomas E.,Killian, Christopher M.,Nile, Terence A.,et al.
, p. 11 - 18 (2007/10/02)
The synthesis of a complete series of substituted 4,5,6,7-tetrahydroindenes (4,5,6,7-tetrahydroindene, 1; 1-methyl-, 1,3-dimethyl- and 1,2,3-trimethyl-4,5,6,7-tetrahydroindene, 2-4) is reported.The synthesis of ferrocenes (8-11) from these substituted cyclopentadienes is described.The electrochemistry of these ferrocenes indicates that these complexes are more readily oxidized than ferrocene and that the effect of methyl or alkyl substituents on the ease of oxidation is additive.A single crystal X-ray structure of two of the ferrocenes, bis(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)iron(II), 10, and bis(1,2,3-trimethyl-4,5,6,7-tetrahydroindenyl)iron(II), 11, indicates that steric hindrance causes the alkyl substituents to be bent away from the plane of the cyclopentadienyl ring.However, the structures differ in that the cyclopentadienyl rings in 10 are staggered whereas those in 11 are eclipsed.The synthesis of the cyclopentadienyltricarbonylmethyl compounds of molybdenum and tungsten from 3 and 4 is also described.Keywords: Iron; Molybdenum; Tungsten; Indenes; Metallocenes; Electrochemistry
Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
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, (2008/06/13)
Disclosed is a process for preparing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, comprising reacting (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound in the presence of a cyanide or a thiocyanate. The cyanide or the thiocyanate is preferably a copper salt. According to the process of the invention, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, which is very useful for the preparation of a metallocene complex catalyst component, can be prepared in a high yield for a short period of time.
