• Bulletin of the Korean Chemical Society
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• v.18 no.5
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• pp.469-471
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• 1997

• Bulletin of the Korean Chemical Society
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• v.24 no.5
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• pp.605-609
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• 2003

The lower-order lithium organocyanocuprate compound, (THF)₃Li(NC)Cu($C_6$H₃-2,6-Mes₂) (1), and the bulky terphenyl Grignard reagent, Br(THF)₂Mg($C_6$H₃-2,6-Trip₂) (2), have been synthesized and structurally characterized both in the solid state by single crystal x-ray crystallography and in solution by multi-nuclear NMR and IR spectroscopy. The compound (1) was isolated as a monomeric contact ion-pair in which the C (organic ipso)-Cu-CN-Li atoms are coordinated linearly. The lithium has a tetrahedral geometry as a result of solvation by three THF molecules. The compound (1) is the first example of fully characterized monomeric lower order lithium organocyanocuprate. The bulky Grignard reagent (2) was also isolated as a monomer in which the magnesium, solvated by two THF molecules, has a distorted tetrahedral geometry. The crystals of (1) possess triclinic symmetry with the space group $P{\={1}}$, Z = 2, with a = 12.456(3) Å, b = 12.508(3) Å, c = 13.904(3) Å, α = 99.81°, β = 103.72(3)°, and γ = 119.44(3)°. The crystals (2) have a monoclinic symmetry of space group $P2_{1/C}$, Z = 4, with a = 13.071(3) Å, b = 14.967(3) Å, c = 22.070(4) Å, and β = 98.95(3)°.

• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.281-284
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• 2007

Neopentyl arenesulfonates react with secondary alkylmagnesium chlorides in the presence of dppfNiCl2 to produce the corresponding arenes via the reductive cleavage of carbon-sulfur bond. Highest yield is obtained by using three equivalents of Grignard reagent to a mixture of arenesulfonate and dppfNiCl2 in Et2O at room temperature. This reaction represents a novel method allowing the efficient hydrogenolysis of sulfur-containing groups in aromatic compounds.

• Bulletin of the Korean Chemical Society
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• v.25 no.11
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• pp.1687-1691
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• 2004

Regioselectivity on the reactions of ${\alpha},{\beta}$--enones with organoindium such as in situ generated allylindium and allenylindium was systematically studied in the presence of TMSCl as an additive. Treatment of 2-cyclohexen-1-one, carvone, 2-cyclohepten-1-one, and chalcone with allylindium reagent produced 1,4-addition products in good yields, while 2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one, 4,4-dimethylcyclohexen-1-one, 3-nonen-2-one, 4-hexen-3-one, and 4-phenyl-3-buten-2-one afforded 1,2-addition products. Indium reagent derived from indium and propargyl bromide in Grignard type gave addition products in good yields, under which the successive addition of ${\alpha},{\beta}$-enone and TMSCl were necessary. Although organoindium reagent derived from propargyl bromide produced propargylated compound in Grignard type except 2-cyclohepten-1-one, indium reagent obtained from 1-bromo-2-butyne having ${\gamma}$-methyl group gave allenylated product inBarbier type.

• Bulletin of the Korean Chemical Society
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• v.20 no.4
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• pp.422-426
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• 1999

The Grignard reactions of bis(chloromethyl)dimethylsilane (1) with trimethylchlorosilane (2) in THF give both the intermolecular C-Si coupling and intramolecular C-C coupling products. At beginning stage, 1 reacts with Mg to give the mono-Grignard reagent ClCH2Me2SiCH2MgCl (1) which undergoes the C-Si coupling reaction to give MC2Si(CH2SiMe3)2 3, or C-C coupling to a mixture of formula Me3SiCH2(SiMe2CH2CH2)nR1 (n = 1, 2, 3, ..; 4a, R1I = H: 4b, R1 = SiMe3). In the reaction, two reaction pathways are involved: a) Ⅰ reacts with 2 to give Me3SiCH2SiMe2CH2Cl 6 which further reacts with Mg to afford a Me2SiCH2Mel-SiCH2MgCl (Ⅱ) or b) I cyclizes intramolecularly to a silacyclopropane intermediate A, which undergoes a ring-opening polymerization by the nucleophilic attack of the intermediates I or Ⅱ, followed by the termination reaction with H2O and 2, to give 4a and 4b, respectively. As the mole ratio of 2/1 increased from 2 to 16 folds, the formation of product 3 increased from 16% to 47% while the formation of polymeric products 4 was reduced from 60% to 40%. The intermolecular C-Si coupling reaction of the pathway a becomes more favorable than the intramolecular C-C coupling reaction of the pathways b at the higher mole ratio of 2/1.

• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1410-1414
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• 2005

Neopentyl arenesulfonates reacted with primary alkylmagnesium halides in the presence of $(PPh_3)_2NiCl_2$ to produce the corresponding alkylarenes. The efficiency of this coupling reaction considerably depends on the nature of catalyst and solvent. Highest yield was obtained by using three equivalents of Grignard reagent to a mixture of $(PPh_3)_2NiCl_2$ and arenesulfonate in refluxing $Et_2O$. This reaction represents a novel method allowing the efficient and creative substitution of sulfur-containing groups in aromatic compounds. It also shows that the alkyloxysulfonyl group might be a suitable alternative to halides and triflate in some circumstances.

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.228-236
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• 1993

The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.

• Journal of the Korean Society of Industry Convergence
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• v.7 no.1
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• pp.107-113
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• 2004

Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

• YAKHAK HOEJI
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• v.36 no.5
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• pp.433-439
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• 1992

For the synthesis of tuberin derivatives, N-(disubstituted styryl) carboxamides, the series of cinnamic acids were transformed through chlorides, azides to isocyanates. And then isocyanates were reduced separately by Dibal and Grignard reagent. As a result of antimicrobial susceptibility test, N-(3,4-dichlorostyryl) formamide and N-(3,4-dichlorostyrl) acetamide showed comparatively large activity against some bacteria that is, MIC was respectively 50 ppm, $6.25{\sim}50\;ppm$. MIC of other derivatives was similiar to that of tuberin, about 100.

• Bulletin of the Korean Chemical Society
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• v.9 no.6
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• pp.379-381
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• 1988

Racemic nuciferal(1) and nuciferol(2), the terpenic natural perfumeries, have been synthesized by a simple procedure. The benzylic halide 6; 1-(1-chloroethyl)-4-methylbenzene, was prepared by converting p-tolualdehyde(4) into 1-(p-tolyl)-1-ethanol(5), followed by convertion of 5 into corresponding chloride. The Grignard reagent of 6 was reacted with the bromoacetal 7, 2-(2-bromoethyl)-1,3-dioxolane, to give a crosscoupling product 8, which was hydrolysed to 4-(p-tolyl)-pentanal (9). The Wittig reaction of isopropylide 10 with 9 yielded arcurcumen(11). The stereospecific allylic oxidation of the gem-dimethyl olefin 11 with selenium dioxide afforded a trans-aldehyde, (${\pm}$)-1, which was reduced to corresponding alcohol, (${\pm}$)-2.