143896-70-2Relevant articles and documents
Twinning-Based Organosuperelasticity and Chirality in a Single Crystal of an Achiral Donor-Acceptor Type Schiff Base Induced by Charge-Transfer Interactions
Sakamoto, Shunichi,Sasaki, Toshiyuki,Takamizawa, Satoshi
, p. 8079 - 8083 (2020)
A charge-transfer (CT) interaction stabilizes molecular assemblies and can form a useful supramolecular synthon in crystal engineering. Herein we demonstrate preparation of a chiral single crystal showing twinning-based organosuperelasticity by forming a CT complex of an achiral donor-acceptor type Schiff base: N-(2,3,4,5,6-pentafluorophenyl)-1-phenylmethanimine. Pseudo-180° symmetry of a single-component CT complex originating from an antiparallel molecular assembly is the key to mechanical twinning. The chiral crystallization induced by CT interactions is also noteworthy because of the potential development of materials showing CT-based functions coupled with chirality.
Visible-Light-Induced Cycloaddition of α-Ketoacylsilanes with Imines: Facile Access to β-Lactams
Ye, Jian-Heng,Bellotti, Peter,Paulisch, Tiffany O.,Daniliuc, Constantin G.,Glorius, Frank
supporting information, p. 13671 - 13676 (2021/05/11)
We report the synthesis of β-lactams from α-ketoacylsilanes and imines, which proceeds via a formal [2+2] photochemical cycloaddition with in situ generation of siloxyketene. This mild and operationally simple reaction proceeds in an atom-economic fashion with broad substrate scope, including aldimines, ketimines, hydrazones, and fused nitrogen heterocycles, affording a variety of important β-lactams with satisfactory diastereoselectivities in most cases. This reaction also features good functional-group tolerance, facile scalability and product diversification. Experimental and computational studies suggest that α-ketoacylsilanes can serve as photochemical precursors by engaging in a 1,3 silicon shift to the distal carbonyl group.
Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis
Junor, Glen P.,Romero, Erik A.,Chen, Xi,Jazzar, Rodolphe,Bertrand, Guy
supporting information, p. 2875 - 2878 (2019/02/13)
Primary aminoboranes (RNHBR2), which are readily available by spontaneous dehydrocoupling of amines and boranes cleanly react at room temperature with aldehydes to give aldimines. The overall transformation from amines to aldimines can be conveniently performed by a sequential one-pot reaction. This synthetic strategy is especially useful for electron poor and bulky amines which are reluctant to react with aldehydes under dehydration conditions. Using a Glorius robustness screen, we show that this methodology is chemoselective, and functional group tolerant. Computational and experimental data support the irreversible formation of the aldimine product in marked contrast with traditional methods.
Benzimidazolium sulfonate ligand precursors and application in ruthenium-catalyzed aromatic amine alkylation with alcohols
Kaloglu, Nazan,?zdemir, Ismail,Gürbüz, Nevin,Achard, Mathieu,Bruneau, Christian
, p. 33 - 38 (2015/11/17)
New benzimidazolium sulfonate salts have been prepared and fully characterized. They have been associated in situ with [RuCl2(p-cymene)]2 to generate efficient catalytic systems operating at 120 °C under neat conditions in the presence of potassium tert-butylate for selective N-alkylation of primary aromatic amines into secondary amines.
Iridium-catalyzed ortho-C-H borylation of aromatic aldimines derived from pentafluoroaniline with bis(pinacolate)diboron
Sasaki, Ikuo,Amou, Tatsunosuke,Ito, Hajime,Ishiyama, Tatsuo
supporting information, p. 2041 - 2044 (2014/03/21)
The development of an Ir-catalyzed ortho-C-H borylation of aromatic aldimines derived from pentafluoroaniline is reported. This reaction proceeded at 120 °C to afford the corresponding borylated products in high yield with good regioselectivity using an I
Isomerization and deuterium scrambling evidence for a change in the rate-limiting step during imine hydrogenation by Shvo's hydroxycyclopentadienyl ruthenium hydride
Casey, Charles P.,Johnson, Jeffrey B.
, p. 1883 - 1894 (2007/10/03)
Hydroxycyclopentadienyl ruthenium hydride 5 efficiently reduces imines below room temperature. Better donor substituents on nitrogen give rise to faster rates and a shift of the rate-determining step from hydrogen transfer to amine coordination. Reduction of electron-deficient N- benzilidenepentafluoroaniline (8) at 11°C resulted in free amine and kinetic isotope effects of kOH/kOD = 1.61 ± 0.08, k RuH/kRuD = 2.05 ± 0.08, and kRuHOH/ kRuDOD = 3.32 ± 0.14, indicative of rate-limiting concerted hydrogen transfer, a mechanism analogous to that proposed for aldehyde and ketone reduction. Reduction of electron-rich N-alkyl-substituted imine, N-isopropyl-(4-methyl)benzilidene amine (9), was accompanied by facile imine isomerization and scrambling of deuterium labels from reduction with 5-RuDOH into the N-alkyl substituent of both the amine complex and into the recovered imine. Inverse equilibrium isotope effects were observed in the reduction of N-benzilidene-tert-butylamine (11) at -48°C (kOH/kOD = 0.89 ± 0.06, kRuH/kRuD = 0.64 ± 0.05, and kRuHOH/kRuDOD = 0.56 ± 0.05). These results are consistent with a mechanism involving reversible hydrogen transfer followed by rate-limiting amine coordination.
Strong phenyl-perfluorophenyl π-π stacking and C-H?F-C hydrogen bonding interactions in the crystals of the corresponding aromatic aldimines
Zhu, Shizheng,Zhu, Shifa,Jin, Guifang,Li, Zhanting
, p. 2713 - 2716 (2007/10/03)
The X-ray diffraction analysis of two co-crystals, 1?2 (aldimines 1 and 2) and 3?4 (aldimines 3 and 4), reveals that there are strong phenyl-perfluorophenyl π-π stacking and intermolecular hydrogen bonding interactions. The new perfluoroaryl-aryl face-to-face interaction of the crystalline aldimines provides a design motif for a new class of self-assembling system.
Synthesis of N-pentafluorophenyl aromatic aldimines C6F5N=CHAr and an X-ray structure analysis of N-pentafluorophenyl-4-methylphenyl aldimine, C6F5N=CHC6H4CH3-4
Li, Aiwen,Bin, Xu,Zhu, Shi-zheng,Huang, Qi-chen,Liu, Jing-song
, p. 145 - 148 (2007/10/02)
N-Pentafluorophenyl aromatic aldimines have been prepared in good yield by the condensation of N-sulfinylpentafluoroaniline (obtained from refluxing pentafluoroaniline with excess thionyl chloride) with aromatic aldehydes.The X-ray structural analysis of
