19490-90-5Relevant articles and documents
Hydrogen Bonding in Diphenylmethanols, RCPh2OH: Structures of Monomeric (4-Biphenyl)diphenylmethanol and Diphenyl(2-pyridyl)methanol, Dimeric 1,1,3-Triphenylpropyn-1-ol, Trimeric 2-Methyl-1,1-diphenylpropan-1-ol, Tetrameric Diphenyl(2-thienyl)methanol, Hexameric Bis(pentafluorophenyl)...
Ferguson, George,Carroll, Christopher D.,Glidewell, Christopher,Zakaria, Choudhury M.,Lough, Alan J.
, p. 367 - 377 (1995)
(4-Biphenyl)diphenylmethanol (1), C25H20O, orthorhombic, P212121, a = 8.3580(11), b = 13.8976(17), c = 15.5915(12) Angstroem, Z = 4, R = 0.032 for 1146 observations 3?(I)>: the structure contains isolated monomers with no hydrogen bonding.Diphenyl(2-pyridyl)methanol (2), C18H15NO, monoclinic, P21/c, a = 8.1899(8), b = 14.855(2), c = 11.6069(15) Angstroem, β = 96.344(8) deg, Z = 4, R = 0.049 for 879 observations 3?(I)>: the structure consists of isolated monomers in which the intramolecular O-H...N hydrogen-bond motif has graph set S(5). 1,1,3-Triphenylpropyn-1-ol (3), C21H16O, monoclinic, P21/c, a = 5.9794 (12), b = 9.953(3), c = 26.420(3) Angstroem, β = 91.365(12) deg, Z = 4, R = 0.039 for 971 observations 2?(I)>: the structure contains centrosymmetric dimers held together by O-H...?(arene) hydrogen bonds involving one of the phenyl groups, rather than the propargyl group. 2-Methyl-1,1-diphenylpropan-1-ol (4), C16H18O, trigonal, P31c, a = 13.9232(17), c = 12.0200(19) Angstroem, Z = 6, R = 0.031 for 763 observations 3?(I)>: the structure consists of cyclic hydrogen-bonded trimers with crystallographic threefold symmetry and disordered hydroxyl H atoms in a motif with graph set R33(6): the O...O distance in the trimers is 2.864(7) Angstroem.Diphenyl(2-thienyl)methanol (5), C17H14OS, rhombohedral, R, a = 19.20(1), c = 26.48(1) Angstroem, Z = 24; this compound is isomorphous and isostructural with triphenylmethanol, Ph3COH, and forms hydrogen-bonded tetrahedral tetramers.Bis(pentafluorophenyl)methanol (6), C13H2F10O, rhombohedral, R, a = 26.113(3), c = 9.788(3) Angstroem (at 293 K), R = 0.068 for 1214 observations 2?(I)>; a = 26.006(4), c = 9.5941(11) Angstroem (at 173 K), R = 0.072 for 1889 observations 2?(I)>, Z = 18; the structure consits of coaxial stacks of cyclic hydrogen-bonded hexamers, each of symmetry, and with a hydrogen-bond motif of graph set R66(12).Within the hexamers, the molecules are disordered over two orientations in the ratio 0.779(3):0.221(3) at 293 K and 0.776(2):0.224(2) at 173 K: the O...O distance is 2.702(4) Angstroem at 293 K and 2.683(4) Angstroem at 173 K.Diphenylmethanol (7), C13H12O, orthorhombic, P22121, a = 5.1300(10), b = 18.650(5), c = 21.168(6) Angstroem, Z = 8, R = 0.035 for 1487 observations 3?(I)>: there are two molecules in the asymmetric unit and the molecules are linked by hydrogen bonds into spiral chains having graph set C(4) and lying parallel to the a-axis; the O...O distances within the chains are 2.826(3) and 2.878(3) Angstroem.
Atom economical coupling of benzophenone and N-heterocyclic aromatics with SmI2
Jaoul, Arnaud,Yang, Yan,Casaretto, Nicolas,Clavaguéra, Carine,Maron, Laurent,Nocton, Grégory
, p. 11875 - 11878 (2020)
The use of stoechiometric SmI2in combination with benzophenone and N-heterocyclic aromatics such as bipyridine, phenanthroline and pyridine allows the directortho-coupling of both partners in an atom economical reaction free of any other coupli
Green synthesis method of polyaryl substituted methanol
-
Paragraph 0127-0131; 0252-0256, (2021/04/17)
The invention relates to a green synthesis method of polyaryl substituted methanol, in particular to a method for efficiently synthesizing polyaryl substituted methanol in a polar aprotic solvent under the condition of an oxidizing agent by taking polyaryl substituted methane as a raw material and alkali as an additive. The method provided by the invention is green and environment-friendly, avoids using expensive metal catalysts, and has the advantages of low cost, few reaction steps, short time, high yield and the like.
(2-Ethylhexyl)sodium: A Hexane-Soluble Reagent for Br/Na-Exchanges and Directed Metalations in Continuous Flow
Annapureddy, Rajasekar Reddy,Harenberg, Johannes H.,Hoefer, Carla A.,Knochel, Paul,Weidmann, Niels,Wiegand, Alexander J.
supporting information, p. 14296 - 14301 (2021/05/07)
We report the on-demand generation of hexane-soluble (2-ethylhexyl)sodium (1) from 3-(chloromethyl)heptane (2) using a sodium-packed-bed reactor under continuous flow conditions. Thus, the resulting solution of 1 is free of elemental sodium and therefore suited for a range of synthetic applications. This new procedure avoids the storage of an alkylsodium and limits the handling of metallic sodium to a minimum. (2-Ethylhexyl)sodium (1) proved to be a very useful reagent and undergoes in-line Br/Na-exchanges as well as directed sodiations. The resulting arylsodium intermediates are subsequently trapped in batch with various electrophiles such as ketones, aldehydes, Weinreb-amides, imines, allyl bromides, disulfides and alkyl iodides. A reaction scale-up of the Br/Na-exchange using an in-line electrophile quench was also reported.
Transition-Metal Free Chemoselective Hydroxylation and Hydroxylation-Deuteration of Heterobenzylic Methylenes
Fu, Yiwei,Li, Hao,Liu, Yonghai,Mang, Zhiguo,Shi, Lei,Sun, Chengyu,Yu, Yang
supporting information, p. 8127 - 8131 (2020/11/03)
We developed an approach for direct selective hydroxylation of heterobenzylic methylenes to secondary alcohols avoiding overoxidation to ketones by using a KOBu-t/DMSO/air system. Most reactions could reach completion in several minutes to give hydroxylated products in 41-76% yields. Using DMSO-d6, this protocol resulted in difunctionalization of heterobenzylic methylenes to afford α-deuterated secondary alcohols (>93% incorporation). By employing this method, active pharmaceutical ingredients carbinoxamine and doxylamine were synthesized in two steps in moderate yields.
Ligand Tuning in Pyridine-Alkoxide Ligated Cp?IrIII Oxidation Catalysts
Sackville, Emma V.,Kociok-K?hn, Gabriele,Hintermair, Ulrich
supporting information, p. 3578 - 3588 (2017/10/03)
Six novel derivatives of pyridine-alkoxide ligated Cp?IrIII complexes, potent precursors for homogeneous water and C-H oxidation catalysts, have been synthesized, characterized, and analyzed spectroscopically and kinetically for ligand effects. Variation of alkoxide and pyridine substituents was found to affect their solution speciation, activation behavior, and oxidation kinetics. Application of these precursors to catalytic C-H oxidation of ethyl benzenesulfonate with aqueous sodium periodate showed that the ligand substitution pattern, solution pH, and solvent all have pronounced influences on initial rates and final conversion values. Correlation with O2 evolution profiles during C-H oxidation catalysis showed these competing reactions to occur sequentially, and demonstrates how it is possible to tune the activity and selectivity of the active species through the NO ligand structure.
An Unprecedented Family of Luminescent Iridium(III) Complexes Bearing a Six-Membered Chelated Tridentate C^N^C Ligand
Hierlinger, Claus,Roisnel, Thierry,Cordes, David B.,Slawin, Alexandra M. Z.,Jacquemin, Denis,Guerchais, Véronique,Zysman-Colman, Eli
, p. 5182 - 5188 (2017/05/08)
A new family consisting of three luminescent neutral Ir(III) complexes with the unprecedented [Ir(C^N^C)(N^N)Cl] architecture, where C^N^C is a bis(six-membered) chelating tridentate tripod ligand derived from 2-benzhydrylpyridine (bnpy) and N^N is 4,4′-di-tert-butyl-2,2′-bipyridine (dtBubpy), is reported. X-ray crystallography reveals an unexpected and unusual double C-H bond activation of the two distal nonconjugated phenyl rings of the bnpy coupled with a very short Ir-Cl bond trans to the pyridine of the bnpy ligand. Depending on the substitution on the bnpy ligand, phosphorescence, ranging from yellow to red, is observed in dichloromethane solution. A combined study using density functional theory (DFT) and time-dependent DFT (TD-DFT) corroborates the mixed charge-transfer nature of the related excited states.
Sodium-Ketyl Radical Anions by Reverse Pinacol Reaction and Their Coupling with Iodoarenes
Tang, Xinjun,Studer, Armido
supporting information, p. 4448 - 4450 (2016/11/07)
Transition-metal-free C-C bond formation between aryl iodides and pinacols is presented. Pinacols are readily transformed by deprotonation with NaH to their Na-pinacolates. C-C-bond homolysis at room temperature generates in situ the corresponding Na-ketyl radical anions which react with various aryl iodides in a homolytic aromatic substitution reaction to form tertiary Na-alcoholates. Protonation eventually provides tertiary alcohols in an unprecedented route.
An efficient synthesis of pyrido[1,2-a]indoles through aza-Nazarov type cyclization
Karthikeyan, Iyyanar,Arunprasath, Dhanarajan,Sekar, Govindasamy
supporting information, p. 1701 - 1704 (2015/03/03)
Transition metal free Br?nsted acid mediated synthesis of biologically important pyrido[1,2-a]indole scaffolds through aza-Nazarov type cyclization of readily available diaryl(2-pyridyl)methanol using formic acid has been developed. This methodology has b
Iron-catalyzed C-H bond functionalization for the exclusive synthesis of pyrido[1,2-a]indoles or triarylmethanols
Karthikeyan, Iyyanar,Sekar, Govindasamy
, p. 8055 - 8063 (2015/01/09)
The efficient and selective iron-catalyzed C-H activation of 2-benzhydrylpyridine derivatives was employed for the preparation of pyrido[1,2-a]indoles through an intramolecular C-H amination reaction. In the presence of molecular oxygen as the sole oxidant, the same 2-benzhydrylpyridines were also used for the synthesis of the corresponding tertiary alcohols. In these approaches, the iron catalyst was used to selectively activate the C(sp2)-H bond of 2-benzhydrylpyridine, in the case of the intramolecular ring-closing C-H amination reaction in which the pyridine nitrogen atom was a directing group as well as a nucleophile, and the C(sp3)-H bond of the same compound, in the case of the oxidation reaction to give the corresponding triaryl carbinol.
