95-13-6Relevant articles and documents
Spontaneous resolution versus formation of racemic crystals of indenylpotassium complexes
Olsson, Susanne,Lennartson, Anders,Hakansson, Mikael
, p. 131 - 135 (2013)
During a study of stereochemically labile organometallic reagents, we found that crystallisation of [K(ind)(pmdta)]n (ind = indenyl, pmdta = N,N,N',N'',N''-pentamethyldiethylenetriamine) from tetrahydrofuran (THF) gave rise to three different crystalline phases depending on the concentration. The more concentrated solutions gave racemic crystals of the previously known coordination polymer [K(ind)(pmdta)]n, a-1. More dilute solutions gave crystals of a new phase, b-1, which was found to undergo spontaneous resolution. From even more dilute solutions, we were able to isolate a chiral inclusion compound with THF, 2, which also undergoes spontaneous resolution. Crystals of b-1 and 2 were enantiomerically pure, and since b-1 is a reactive organometallic reagent, attempts were made to use the crystals in enantioselective synthesis. Reacting single crystals with N-chlorosuccinimide gave rise to chiral 1-chloroindene, but no enantiomeric excess was observed.
Synthesis of borylindenides; Structure of [Li(N,N′,N″-Me3-1,3,5-C3H6N 3)][1-C9H6{B(NMe2)2}]
Herberich, Gerhard E.,Barday, Estelle,Fischer, Andreas
, p. 127 - 131 (1998)
Borylation of lithium indenide (LiInd) affords indenylboranes. With BCl(NMe2)2 the primary allylic 1-indenyl derivative IndB(NMe2)2 (1) readily rearranges to the more stable vinylic bis(dimethylamino)(3-indenyl)borane 1′. With BCl(OCMe2)2 the (1-indenyl)-1,3,2-dioxaborolane IndB(OCMe2)2 (2) is obtained. Both indenylboranes 1′ and 2 readily undergo metalation when treated with lithium amides such as LiTMP or LDA to give 1-borylindenides Li[C9H6B(NMe2)2] [Li(3)] and Li[C9H6B(OCMe2)2] [Li(5)] in high yields. In the systems 1′/LiInd and 2/LiInd metalation equilibria are established with equlibrium constants K≈1 (1'/LiInd) and K≈1.4 (2/LiInd). The structure of the solvate [Li(TMHT)][1-C9H6{B(NMe2)2}] (4) (TMHT=N,N',N''-Me3-1,3,5-C3H6N3) has been confirmed by X-ray diffraction.
INDENODIAZETINE: PREPARATION AND THERMAL DIAZETATION
Pincock, J. A.,Druet, Linda M.
, p. 3251 - 3252 (1980)
The preparation of an aryl substitued diazetine and the kinetics for its thermal decomposition to nitrogen and alkene are reported.
Can N-alkyl- and N-arylimidazoles be prepared directly from alcohols and phenols with N,N'-carbonyldiimidazole?
Fischer
, p. 29 - 30 (2002)
The report that N-alkyl- and N-arylimidazoles can be prepared directly by reactions of N,N'-carbonyldiimidazole (CDI) with alcohols or phenols was shown to be erroneous. Under the described conditions only (N-alkoxy-carbonyl)- and (N-aryloxy-carbonyl)-imi
Mehrfachbindungen zwischen Hauptgruppenelementen und Uebergangsmetallen. CXLIII. Indenyltrioxorhenium(VII): Organometalloxid mit dynamischer Struktur
Herrmann, Wolfgang A.,Kuehn, Fritz E.,Romao, Carlos C.
, p. C56 - C59 (1995)
Indenyltrioxorhenium(VII), (C9H7)ReO3, was synthesized from Re2O7 and (indenyl)tris(n-butyl)tin.It is a moisture- and temperature-sensitive compound (dec. -30 deg C), the structure of which adopts η1-coordination of the organic ligand.According to 1H NMR studies, a haptotropic structural rearrangement occurs at > -25 deg C in solution (1,3-shift mechanism).Decomposition studies show a concentration decay of the title compound in anhydrous solution, with formation of ReO3 and indene.Keywords: Rhenium; Indenyl; Dynamic structure; NMR
Electro-mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions
Barham, Joshua P.,K?nig, Burkhard,Karl, Tobias A.,Reiter, Sebastian,Tian, Xianhai,Yakubov, Shahboz,de Vivie-Riedle, Regina
, p. 20817 - 20825 (2021/08/18)
We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)?O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)?O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.
A donor-acceptor complex enables the synthesis of: E -olefins from alcohols, amines and carboxylic acids
Chen, Kun-Quan,Shen, Jie,Wang, Zhi-Xiang,Chen, Xiang-Yu
, p. 6684 - 6690 (2021/05/31)
Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor-acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.
Mild olefin formationviabio-inspired vitamin B12photocatalysis
Bam, Radha,Pollatos, Alexandros S.,Moser, Austin J.,West, Julian G.
, p. 1736 - 1744 (2021/02/22)
Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B12-dependent photoreceptor CarH, where photolysis of a cobalt-carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B12-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B12to be a powerful platform for developing mild olefin-forming reactions.
Mild and efficient desulfurization of thiiranes with MoCl5/Zn system
Lee, Yeong Jin,Shin, Jeong Won,Yoo, Byung Woo
, (2021/11/10)
Desulfurization of a variety of thiiranes to alkenes occurs chemoselectively in high yields upon treatment with MoCl5/Zn system under mild conditions. The new methodology demonstrates high functional group tolerance toward chloro, bromo, fluoro, methoxy, ester, ether and keto groups.
INDENE COMPOSITION
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Paragraph 0107-0109, (2022/01/08)
The present invention provides an indene composition having a content of indene of 80 to 99.5% by mass, in which a content ratio of a hydrocarbon compound having a condensed ring structure of a 5-membered ring and a 6-membered ring, and having 9 or 10 carbon atoms, in a component contained in addition to indene, is 90% by mass or more, and a content of benzonitrile is 0.5% by mass or less, and a content of sulfur is 5 ppm by mass or less.
