Titanium(IV) Lewis Acids

Urabe, Hirokazu; Sato, Fumie

doi:10.1002/9783527618309.ch15

Cited by 19 publications

(8 citation statements)

References 636 publications

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“…The use of titanium-based Lewis acids to activate stabilized carbon nucleophiles for attack on any number of electrophiles is a well-established tactic, [55] and the use of chiral ligands to effect these transformations enantioselec-tively is similarly well documented. [56] It is not surprising, then, that when the electrophile is an iodiranium ion, the reaction would proceed with high enantioselectivity.…”

Section: Type Iv: Lewis Acid Catalyzed or Directed Halocyclizationmentioning

confidence: 99%

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

2012

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Despite the fact that halogenation of alkenes has been known for centuries, enantioselective variants of this reaction have only recently been developed. In the past three years, catalytic enantioselective versions of halofunctionalizations with the four common halogens have appeared and although important breakthroughs, they represent just the very beginnings of a nascent field. This Minireview provides a critical analysis of the challenges that accompany the development of general and highly enantioselective halofunctionalization reactions. Moreover, the focus herein, diverges from previous reviews of the field by identifying the various modes of catalysis and the different strategies implemented for asymmetric induction.

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Section: Type Iv: Lewis Acid Catalyzed or Directed Halocyclizationmentioning

confidence: 99%

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

2012

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“…The titanium complexes based on these ligands, and among them, those with the general formula Ti(OR) 2 Cl 2 or Ti(OR) 4 have been known for a while and are used as Lewis acid catalysts or at stoichiometric amounts for a wide scope of organic reactions such as hetero-Diels-Alder reactions, Michael additions, and others. 40 Simple titanium alkoxide complexes are used as well in the epoxidation of olefins. 41 The complexes in which R shows a specific chirality are of particular interest for enantioselective transformations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Dichlorotitanium Alkoxide Complex and Its Activity in the Polymerization of α-Olefins

et al. 2007

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We present the synthesis, characterization, X-ray molecular structure, and catalytic activity of a [(HOEt)Ti(µ-OEt)OEt(Cl) 2 ] 2 (1) dimeric complex. Complex 1 was found to undergo, in solution, a succession of fluxional processes involving the rotation of the ligands, rapid exchange between the anionic ethoxide ligands, and exchange of the hydroxylic hydrogen. The complex, when activated by methylalumoxane (MAO), undergoes an abstraction of the ligands through a heterobimetallic intermediate with ethoxide bridges between the aluminum and titanium atoms. We propose that this intermediate is the active species in the polymerization of R-olefins. The complex displays unexpectedly a single site behavior in contradiction to other titanium alkoxide complexes. The resulting polymers were found to show elastomeric properties with intermediate tacticities.

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“…The reaction was catalyzed by the Lewis acid tetraisopropyl orthotitanate (0.2 wt% loading) based on a method reported in the patent literature, Scheme 1. 46,47 Careful distillation to remove the low boiling, by-product methanol steered the equilibrium by Le Châtelier's principle in favor of the higher carbonate. 48 Some unreacted isoamyl alcohol was next distilled away and nally the DFC was collected without any fractionation.…”

Section: Synthesis Of Difusel Carbonatementioning

confidence: 99%

Solubility of hydrocarbon oils in alcohols (≤C₆) and synthesis of difusel carbonate for degreasing

et al. 2019

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The empirical solubility of hydrocarbon fluids, polyalphaolefin (PAO) and mineral oil, in thirteen small molecular weight alcohols (C 1 -C 6 ) was determined. Butanols, pentanols, and 1-hexanol could dissolve up to PAO-10 and mineral oil. tert-Pentanol and 1-hexanol could also dissolve high-viscosity PAO-150.The dialkyl carbonate of fusel oil (DFC) was synthesized from dimethyl carbonate in 69% yield. DFC had excellent non-polar solubility and could dissolve PAO-150 and several common industrial lubricants. The flash point of DFC was 93 C, more than twice that of isoamyl alcohol. DFC had net heating value of 30.47 MJ kg À1 , nearly double that of dimethyl carbonate. However, its derived cetane number of 22.8 indicates DFC could not be used directly as diesel fuel.

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Titanium(IV) Lewis Acids

Cited by 19 publications

References 636 publications

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

Synthesis and Characterization of Dichlorotitanium Alkoxide Complex and Its Activity in the Polymerization of α-Olefins

Solubility of hydrocarbon oils in alcohols (≤C₆) and synthesis of difusel carbonate for degreasing

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Titanium(IV) Lewis Acids

Cited by 19 publications

References 636 publications

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

Catalytic, Asymmetric Halofunctionalization of Alkenes—A Critical Perspective

Synthesis and Characterization of Dichlorotitanium Alkoxide Complex and Its Activity in the Polymerization of α-Olefins

Solubility of hydrocarbon oils in alcohols (≤C6) and synthesis of difusel carbonate for degreasing

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Solubility of hydrocarbon oils in alcohols (≤C₆) and synthesis of difusel carbonate for degreasing