7789-48-2Relevant academic research and scientific papers
Magnesium Halide-promoted Ring-opening Reaction of Cyclic Ether in the Presence of Phosphine Halide
Chang, Yu-Chang,Weng, Chia-Ming,Shaikh, Tanveer M.,Hong, Fung-E
, p. 703 - 711 (2015)
A new route to the direct preparation of H-phosphinate esters has been explored. The ring-opening reaction of cyclic ether (tetrahydrofuran or tetrahydropyrane) was carried out with magnesium halide in the presence of phosphine halide (PRCl2 or PCl3). The process is straightforward and all the reagents are relatively cheap and readily available. Magnesium halide-mediated THF ring-opening (SN2@C) and the subsequent SN2@P elementary reactions that giving rise to the intermediate of haloalkyl phosphinates have been discussed based on our experimental findings (Path I: SN2@C-+SN2@P). Another possible route, the direct SN2 between THF (nucleophile) and phosphine halide (electrophile) that followed by THF ring opening by halide dissociated from phosphine halide (Path II: SN2@P-+SN2@C), was also proposed. However, path II is the least likely reaction path because neutral THF is not a good nucleophile. H-phosphinate esters could be readily available in the subsequent hydrolysis process. Considering the ionic bond strength in magnesium halides and the nucleophilicity of halides dissociated from MgX2 in protic solvents like water, MgBr2 is recommended for ring-opening reactions of cyclic ethers.
Iron-catalyzed δ-selective conjugate addition of methyl and cyclopropyl Grignard reagents to α,β,γ,δ-unsaturated esters and amides
Sugano, Goshi,Kawada, Kojiro,Shigeta, Masayuki,Hata, Takeshi,Urabe, Hirokazu
, p. 885 - 890 (2019)
Iron-catalyzed δ-selective conjugate addition of methyl and cyclopropyl Grignard reagents to α,β,γ,δ-unsaturated esters and amides took place in good yields to give products exclusively with cis-β,γ-olefinic bond.
Uniaxial orientational order-disorder transitions in diammine magnesium halides, Mg(ND3)2Cl2 and Mg (ND3)2Br2, investigated by neutron diffraction
Leineweber,Jacobs,Fischer,Boettger
, p. 487 - 499 (2001)
Neutron powder diffraction on Mg(ND3)2Cl2 and Mg(ND3)2Br2 revealed as a function of temperature uniaxial orientational order-disorder behavior of the ND3 groups. The crystal structures of both compounds are built up from chains of octahedra ∞1[Mg(NH3)2X4/2] with X=Cl and Br arranged in different ways relative to each other. At ambient temperatures (X=Cl) and 270 K (X=Br) the ND3 groups are disordered with respect to a rotation about the bond Mg-N. The D atom density is well described by a fourfold split position, each D site connecting an N with an X atom: Mg(ND3)2Cl2, Cmmm, a=8.1828(6) A, b=8.2007(6) A, c=3.7543(2) A, R(F2)Bragg=5.9%; Mg(ND3)2Br2, Pbam, a=5.9714(2) A, b=11.9175(3) A, c=3.98477(8) A, R(F2)Bragg=7.9%. In both cases the c axis corresponds to the direction of the chains ∞1[Mg(NH3)2X 4/2]. At low temperatures (8 K (X=Cl) and 1.5 K (X=Br)) both compounds are ordered with respect to the ND3 groups: They are arranged antiferroelectrically on either side of the chains ∞1[Mg(NH3)2X 4/2]. The symmetry is lowered compared to the situation at ambient temperatures and 270 K respectively, which involves in both cases a doubling of the orthorhombic c axis: Mg(ND3)2Cl2, Ibmm, a=8.1319(3) A, b=8.1338(3) A, c=7.4410(2) A, R(F2)Bragg=5.9%; Mg(ND3)2Br2, Pnam, a=5.92837(8) A, b=11.8448(2) A, c=7.9117(1) A, R(F2)Bragg=5.0%. Detailed evaluation of neutron diffraction data of Mg(ND3)2Cl2 as a function of temperature (50 Kt ≈ 135K.
Protonation of Imines by Water in the Presence of Salts: Role of Cooperative Effects in Water-Shared Ion Pairs
Corset, J.,Froment, F.
, p. 6908 - 6911 (1990)
An IR spectroscopic study of lithium and magnesium salt solutions in acetonitrile in the presence of an organic base such 1,8-diazabicycloundec-7-ene (DBU) shows that this base may be protonated by water when added.The formation of a water-separated ion pair is essential to this protonation.The replacement of a solvent molecule by a DBU molecule in the first solvation shell of the cation in this solvent-separated ion pair leads to the elimination of protonated DBUH+X- ion pair.
Chemistry of c-trimethylsilyl-substituted heterocarboranes. 23. synthetic, spectroscopic, and structural investigation on half- and full-sandwich Magnesacarboranes of 2,3- and 2,4-C2B4 carborane ligands
Hosmane, Narayan S.,Zhu, Dunming,McDonald, James E.,Zhang, Hongming,Maguire, John A.,Gray, Thomas G.,Helfert, Sarah C.
, p. 1426 - 1437 (1998)
The reaction of nido-1-Na(L)n-2-(SiMe3)-3-(R)-2,3-C2B 4H5 (n = 2, L = THF, R = SiMe3; n = 1, L = TMEDA, R = SiMe3 or Me) or closo-exo-5,6-[(μ-H)2Li(L)n]-1-Li(L) n-2,4-(SiMe3)2-2,4-C2B 4H4 (n = 2, L = THF; n = 1, L = TMEDA) with various magnesium reagents produced a number of different magnesacarboranes. The product of a 1:1 molar ratio reaction of the 2,3-C2B4 monosodium compound (R = SiMe3 and L = TMEDA) with MeMgBr was the half-sandwich magnesacarborane closo-1-Mg(TMEDA)-2,3-(SiMe3)2-2,3-C2B 4H4 (I), while when R = Me, the same reaction conditions gave the novel full-exo-sandwich complex commoexo-4,4′,5,5′-Mg(TMEDA)[2-(SiMe3)-3-(Me)-2,3-C 2B4H5]2 (II). The full-endo-sandwich magnesacarboranes [Na(THF)2]2[commo-1,1′-Mg{2,3-(SiMe 3)2-2,3-C2B4H4} 2] (IV) and [Na-(TMEDA)]2[commo-1,1′-Mg{2,3-(SiMe3) 2-2,3-C2B4H4}2] (V) were the exclusive products when the appropriate monosodium compound reacted with Mg(Bu)2 in 2:1 molar ratios. Reaction of closo-exo-5,6-[(μ-H)2Li(TMEDA)]-1-Li(TMEDA)-2,4-(SiMe 3)2-2,4-C2B4H4 with MgBr2 in a 1:1 molar ratio produced closo-1-Mg(TMEDA)-2,4-(SiMe3)2-2,4-C2B 4H4 (III), while a 2:1 molar ratio gave [Li(TMEDA)2]2[commo-1,1′-Mg{2,4-(SiMe 3)2-2,4-C2B4H4} 2] (VI). The yields ranged from 73% for III to 94% for II. On the other hand, the 1:1 molar ratio reaction of the THF-solvated 2,4-C2B4 disodium compound with MeMgBr, followed by the addition of 1 equiv of the THF-solvated monosodium compound of the 2,3-C2B4 carborane did not give the expected mixed-ligand complex but produced a 50:50 mixture of IV and [Li(THF)2]2[commo-1,1′-Mg-{2,4-(SiMe 3)2-2,4-C2B4H4} 2] (VII) in nearly quantitative yields. The magnesacarboranes were characterized by their infrared spectra, chemical analysis, H1, 11B, and 13C NMR spectra, and, in the case of VII, by its 7Li NMR spectrum. Compounds I, II, and IV were further characterized by single-crystal X-ray analysis. Compound I crystallizes as a dimer in which a Mg occupies the apical position above the pentagonal face of one carborane and is bonded to the unique boron of the other carborane in the dimer through a Mg-H-B bridge. The structure of II is one in which a TMEDA-solvated Mg is exo-polyhedrally bonded to two 2,3-C2B4 monoanionic ligands through a pair of Mg-H-B bridges, while in IV, the two carborane dianions are η5-bonded to a Mg in a more conventional endo-sandwich complex. The reactions with MeMgBr are thought to proceed through the formation of a methylmag-nesacarborane intermediate which undergoes further reaction to give the final products. The 11B NMR spectra of I-VII were analyzed with the aid of ab initio GIAO molecular orbital calculations.
Synthesis and synthetic applications of (4-hydroxyphenyl)perfluoroalkylmethanols
Terashima, Kyu,Kawasaki-Takasuka, Tomoko,Minami, Ichiro,Yamazaki, Takashi
, (2021/12/03)
Development of the convenient method for the synthesis of (hydroxyphenyl)perfluoro-alkylmethanols was achieved by the Meerwein-Ponndorf-Verley (MPV) type reduction of the in situ-generated perfluoroalkylated ketones as the key step. The benzylic OH group of the resultant alcohols was successfully converted to H or Rf(CH2)nO by way of the corresponding chlorides, this transformation being not easy by any other methods.
Aziridine Ring Opening as Regio-and Stereoselective Access to C-Glycosyl-Aminoethyl Sulfide Derivatives
Le?niak, Stanis?aw,Malinowska, Martyna,Tracz, Aleksandra,Zawisza, Anna
, (2022/03/23)
A short synthetic route to stereoselective access to C-glycosyl-aminoethyl sulfide derivatives has been developed through the reaction of tributhyltin derivatives of glycals with aziridinecarboaldehyde and the regioselective ring opening of a chiral aziridine with thiophenol. The absolute configurations of the resulting diastereoisomers were determined by 1H NMR spectroscopy.
Nickel-Catalysed Allylboration of Aldehydes
Dennis, Francesca M.,Partridge, Benjamin M.,Robertson, Craig C.
, p. 1903 - 1914 (2020/07/04)
A nickel catalyst for the allylboration of aldehydes is reported, facilitating the preparation of homoallylic alcohols in high diastereoselectivity. The observed diastereoselectivities and NMR experiments suggest that allylation occurs through a well-defined six-membered transition state, with nickel acting as a Lewis acid.
Copper-Catalyzed Regio- and Enantioselective Addition of Silicon Grignard Reagents to Alkenes Activated by Azaaryl Groups
Mao, Wenbin,Xue, Weichao,Irran, Elisabeth,Oestreich, Martin
supporting information, p. 10723 - 10726 (2019/07/04)
A new application of silicon Grignard reagents in C(sp3)?Si bond formation is reported. With the aid of BF3?OEt2, these silicon nucleophiles add across alkenes activated by various azaaryl groups under copper catalysis. An enantioselective version employing benzoxazole-activated alkenes as substrates and a CuI-josiphos complex as catalyst has been developed, forming the C(sp3)?Si bond with good to high enantiomeric ratios (up to 97:3). The method expands the toolbox for “conjugate addition” type C(sp3)?Si bond formation.
Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
Xue, Weichao,Oestreich, Martin
, p. 233 - 239 (2019/01/04)
A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti -dia-stereoselectivity was obtained.
