215715-81-4Relevant academic research and scientific papers
Hydrogen-bonded networks in oxygen-coordinated monoamide complexes of zinc(II)
Mokhtabad Amrei, Leila,Boeré, René T.
, p. 621 - 628 (2018)
The preparation of the bulky secondary amide N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamide and the determination of its crystal structure at 173(2) K are reported. The structure displays disorder of the tBu methyl groups due to thermal motion and an infinite N-H····O=C hydrogen-bonded chain described by a graph set. Reaction of this amide with ZnCl2 or ZnBr2 in tetrahydrofuran (THF) results in dihalo-(tetrahydrofurano)-(N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamido)-zinc(II) complexes (Cl, Br) for which the crystal structures have also been determined. These complexes, as well as a chloroform solvate of the dichloro-complex, contain N-H····X-Zn hydrogen-bonded chains described by graph sets. Evaporative crystallization results in the loss of both chloroform and THF to afford crystals determined to be bis(μ2-chloro)-dichloro-bis(N-(2,6-diisopropylphenyl)-2,2-dimethylpropanamido)-dizinc(II) by single crystal X-ray diffraction. This dimeric complex shows a complex network of N-H····Cl-Zn hydrogen bonds describable by, and chains, small molecular squares , and larger rings.
Surprisingly Different Reaction Behavior of Alkali and Alkaline Earth Metal Bis(trimethylsilyl)amides toward Bulky N-(2-Pyridylethyl)-N′-(2,6-diisopropylphenyl)pivalamidine
Kalden, Diana,Oberheide, Ansgar,Loh, Claas,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
, p. 10944 - 10959 (2016)
N-(2,6-Diisopropylphenyl)-N′-(2-pyridylethyl)pivalamidine (Dipp-N=C(tBu)-N(H)-C2H4-Py) (1), reacts with metalation reagents of lithium, magnesium, calcium, and strontium to give the corresponding pivalamidinates [(tmeda)Li{Dipp-N=C(tBu)-N-C2H4-Py}] (6), [Mg{Dipp-N=C(tBu)-N-C2H4-Py}2] (3), and heteroleptic [{(Me3Si)2N}Ae{Dipp-N=C(tBu)-N-C2H4-Py}], with Ae being Ca (2 a) and Sr (2 b). In contrast to this straightforward deprotonation of the amidine units, the reaction of 1 with the bis(trimethylsilyl)amides of sodium or potassium unexpectedly leads to a β-metalation and an immediate deamidation reaction yielding [(thf)2Na{Dipp-N=C(tBu)-N(H)}] (4 a) or [(thf)2K{Dipp-N=C(tBu)-N(H)}] (4 b), respectively, as well as 2-vinylpyridine in both cases. The lithium derivative shows a similar reaction behavior to the alkaline earth metal congeners, underlining the diagonal relationship in the periodic table. Protonation of 4 a or the metathesis reaction of 4 b with CaI2in tetrahydrofuran yields N-(2,6-diisopropylphenyl)pivalamidine (Dipp-N=C(tBu)-NH2) (5), or [(thf)4Ca{Dipp-N=C(tBu)-N(H)}2] (7), respectively. The reaction of AN(SiMe3)2(A=Na, K) with less bulky formamidine Dipp-N=C(H)-N(H)-C2H4-Py (8) leads to deprotonation of the amidine functionality, and [(thf)Na{Dipp-N=C(H)-N-C2H4-Py}]2(9 a) or [(thf)K{Dipp-N=C(H)-N-C2H4-Py}]2(9 b), respectively, are isolated as dinuclear complexes. From these experiments it is obvious, that β-metalation/deamidation of N-(2-pyridylethyl)amidines requires bases with soft metal ions and also steric pressure. The isomeric forms of all compounds are verified by single-crystal X-ray structure analysis and are maintained in solution.
Hydroboration Catalyzed by 1,2,4,3-Triazaphospholenes
Tien, Chieh-Hung,Adams, Matt R.,Ferguson, Michael J.,Johnson, Erin R.,Speed, Alexander W. H.
supporting information, p. 5565 - 5568 (2017/10/25)
The synthesis and study of the catalytic activity of 1,2,4,3-triazaphospholenes (TAPs) is reported. TAPs represent a more modular scaffold than previously reported diazaphospholenes. TAP halides were shown to catalyze the 1,2 hydroboration of 19 imines, and three α,β unsaturated aldehydes with pinacolborane, including examples that did not undergo hydroboration by previously reported diazaphospholene systems. DFT calculations support a mechanism where a triazaphospholene cation interacts with the substrate, a mechanism distinct from diazaphospholene catalyzed hydroborations.
Bis(imino)phosphanes: Synthesis and Coordination Chemistry
Van Dijk, Tom,Rong, Mark K.,Borger, Jaap E.,Nieger, Martin,Slootweg, J. Chris,Lammertsma, Koop
, p. 827 - 835 (2016/03/30)
Bis(imino)phosphanes can be synthesized efficiently from iminophosphanes and nitrilium triflates, allowing for nonsymmetric substitution at the imine groups. Symmetrically substituted derivatives can even be obtained in a one-pot procedure from primary ph
Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
, p. 4602 - 4605 (2016/09/28)
A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
Synthesis of 1,2-borazaronaphthalenes from imines by base-promoted borylation of C-H bond
Liu, Xinwang,Wu, Pengbo,Li, Jianfeng,Cui, Chunming
, p. 3737 - 3744 (2015/05/05)
A new route from benzylic imines permits the synthesis of 1,2-borazaronaphthalenes in good yields. The reaction involves formation of the enamidyl dibromoborane, which undergoes base-promoted borylation of the nearby aromatic C-H bond. Electrophilic attack of the boron species onto the benzylic arene is supported by the slow borylation of arenes substituted with electron-withdrawing groups. The resultant boron bromides can be easily substituted with lithium reagents to provide a range of products. The electronic properties of these 1,2-borazaronaphthalene derivatives have been investigated by UV-vis and fluorescence spectroscopy.
Structural evidence of strong calcium-π interactions to aryl substituents stabilized by coexistent agostic bonds to alkyl groups
Loh, Claas,Seupel, Susanne,Goerls, Helmar,Krieck, Sven,Westerhausen, Matthias
, p. 1480 - 1491 (2014/04/17)
Metalation of 1-(2-furanylmethyl)-(1a) and 1-(2-pyridylmethyl)-2-tert- butyl-3-(2,6-diisopropylphenyl)-1,3-diazaprop-2-ene (1b) with n-butyllithium and potassium bis(trimethylsilyl)amide in tetrahydrofuran (THF) yields the corresponding lithium (2a,b) and potassium derivatives (3a,b), with the alkali metals binding to the furanylmethylamido and pyridylmethylamido pockets. The calcium derivatives are accessible via a metathetical approach of the potassium complexes with calcium iodide in THF. Whereas bis[1-(2-furanylmethyl)-2-tert- butyl-3-(2,6-diisopropylphenyl)-1,3-diazaallyl]calcium (4a) precipitates as a thf adduct, bis[1-(2-pyridylmethyl)-2-tert-butyl-3-(2,6-diisopropylphenyl)-1,3- diazaallyl]calcium (4b) crystallized without solvent coligands. Instead of coordinated solvent molecules, strong calcium-π interactions to an aryl group saturate the coordination sphere. Bidentate 1,2-dimethoxyethane (DME), however, is able to replace this side-on bound aryl group, leading to the dme adduct of bis[1-(2-pyridylmethyl)-2-tert-butyl-3-(2,6-diisopropylphenyl)-1,3-diaallyl] calcium (4c). In all of these s-block metal complexes, strong agostic interactions between the cations and the tert-butyl groups stabilize these complexes.
N,N′-Bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidinates of the s-block metals lithium, potassium, and calcium
Loh, Claas,Seupel, Susanne,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
supporting information, p. 1312 - 1321 (2014/04/03)
Metalation of N,N′-bis(2,6-diisopropylphenyl)benzamidine (1a) and -pivalamidine (1b) in tetrahydrofuran (THF) with n-butyllithium and potassium bis(trimethylsilyl)amide gives the corresponding N,N′-bis(2,6- diisopropylphenyl)benzamidinates and -pivalamidi
N,N′-Bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidinates of the s-block metals lithium, potassium, and calcium
Loh, Claas,Seupel, Susanne,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
supporting information, p. 1312 - 1321 (2015/04/27)
Metalation of N,N′-bis(2,6-diisopropylphenyl)benzamidine (1a) and -pivalamidine (1b) in tetrahydrofuran (THF) with n-butyllithium and potassium bis(trimethylsilyl)amide gives the corresponding N,N′-bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidin
Titanium pyridonates and amidates: Novel catalysts for the synthesis of random copolymers
Webster, Ruth L.,Noroozi, Nazbanoo,Hatzikiriakos, Savvas G.,Thomson, Jaclyn A.,Schafer, Laurel L.
supporting information, p. 57 - 59 (2013/02/22)
A series of pyridonate and amidate supported titanium alkoxides have been isolated. These complexes can be readily prepared in high yield, under mild reaction conditions in only two steps from commercially available (Ti(NMe 2)4). We
