115976-33-5

Upstream product

• 98-86-2 acetophenone 
• 1445-91-6 (S)-1-phenylethanol 
• 1517-69-7 (R)-1-phenylethanol 
• 98-85-1 1-Phenylethanol 
• 4545-21-5 acetophenone p-toluenesulfonylhydrazone 
• 22739-76-0 d8-isopropanol 

Downstream Products

• 71886-64-1 (S)-α-Deuterio-α-phenylethanol 
• 98-86-2 acetophenone 
• 1203578-65-7 7-bromo-2-phenylquinoline 
• 60301-56-6 6-chloro-2-phenylquinoline 
• 61687-26-1 7-chloro-2-phenyl-quinoline 
• 27356-46-3 6-methyl-2-phenyl-quinoline 
• 5353-90-2 8-methyl-2-phenylquinoline 
• 612-96-4 2-Phenylquinoline 

Relevant academic research and scientific papers

Mechanistic investigations of the palladium-catalyzed aerobic oxidative kinetic resolution of secondary alcohols using (-)-Sparteine

The mechanistic details of the Pd(II)/(-)-sparteine-catalyzed aerobic oxidative kinetic resolution of secondary alcohols were elucidated, and the origin of asymmetric induction was determined. Saturation kinetics were observed for rate dependence on [(-)-sparteine]. First-order rate dependencies were observed for both the Pd((-)-sparteine)Cl2 concentration and the alcohol concentration at high and low [(-)-sparteine]. The oxidation rate was inhibited by addition of (-)-sparteine HCl. At low [(-)-sparteine], Pd-alkoxide formation is proposed to be rate limiting, while at high [(-)-sparteine], β-hydride elimination is proposed to be rate determining. These conclusions are consistent with the measured kinetic isotope effect of kH/kD = 1.31 ± 0.04 and a Hammett ρ value of -1.41 ± 0.15 at high [(-)-sparteine]. Calculated activation parameters agree with the change in the rate-limiting step by increasing [(-)-sparteine] with ΔH? = 11.55 ± 0.65 kcal/ mol, ΔS? = -24.5 ± 2.0 eu at low [(-)-sparteine], and ΔH? = 20.25 ± 0.89 kcal/mol, ΔS? = -5.4 ± 2.7 eu at high [(-)-sparteine]. At high [(-)-sparteine], the selectivity is influenced by both a thermodynamic difference in the stability of the diastereomeric Pd-alkoxides formed and a kinetic β-hydride elimination to maximize asymmetric induction. At low [(-)-sparteine], the selectivity is influenced by kinetic deprotonation, resulting in lower krel values. A key, nonintuitive discovery is that (-)-sparteine plays a dual role in this oxidative kinetic resolution of secondary alcohols as a chiral ligand on palladium and as an exogenous chiral base.

Rh(III)Cp? and Ir(III)Cp? Complexes of 1-[(4-Methyl)phenyl]-3-[(2-methyl-4′-R)imidazol-1-yl]triazenide (R = t-Bu or H): Synthesis, Structure, and Catalytic Activity

A series of iridium and rhodium complexes have been synthesized using as ligand a triazenide monofunctionalized with an imidazole substituent. Steric hindrance at the imidazole moiety induced differences in the coordination modes as well in the catalytic behavior of complexes 4-7. Complexes 4-7 were tested in the transfer hydrogenation of acetophenone and 5-alken-2-ones. The hydrogenation of either the double bond or the carbonyl group in 5-alken-2-ones, showed to be selective in the presence of 6, 7, and 10 and has a dependence on the presence or absence of base. Control experiments point out that the imidazole moiety in the structure of complexes 4-7 speeds-up the catalysis.

A comparative study of the McMurry reaction utilizing x, TiCl3(DME)1.5-Zn(Cu) and TiCl2 * LiCl as coupling reagents

An investigation of the reaction course and stoichiometry of the McMurry reaction of acetophenone utilizing x (THF=tetrahydrofuran), TiCl3(DME)1.5-Zn(Cu) (DME=1,2-dimethoxyethane) and TiCl2*LiCl as coupling reagents has been undertaken.The detection of 1-phenylethanol (3a) or dideutero-1-phenylethanol (3b) (Schemes 1 and 3) as hydrolysis or deuterolysis products in the early stage of reactions gave the first direct experimental evidence for the occurence of the "side-on" bonded ketones 3 and 3" as possible precursors of the pinacolates 4 and 7.This result supports the nucleophilic rather than the radical mechanism for the C-C coupling step of aromatic ketones.Contrary to the current opinion, upon refluxing TiCl3(DME)1.5-Zn(Cu) mixtures in DME, no reduction of Ti3+ to low valence Ti species could be detected.The reduction of Ti3+ by Zn (Scheme 2) only starts in the presence of the carbonyl substrate which is coordinated to the Ti (the "instant method"); both the ketone-> pinacolate and the pinacolate-> alkene steps (Scheme 2) apparently involve a transient reduction of Ti3+ by Zn.This view is supported by experiments in which TiCl2*LiCl is used as a reagent and in which it behaves as a one-electron reductant (Scheme 3).On the basis of these results, the overall stoichiometry of the McMurry reaction utilizing TiCl3(DME)1.5-Zn(Cu) as a reagent can be represented by Eq. (4).High yields (95-97percent) of the alkene 2 in acceptable reaction times can already be achieved with an acetophenone: TiCl3(DME)1.5:Zn(Cu) molar ratio of 1:2:2.A conclusion which can be drawn from the results is that the McMurry reaction when performed with two of the most commonly applied reagents, namely TiCl3-LiAlH4-THF (in fact HTiCl(THF)0.5!) and TiCl3(DME)1.5-Zn(Cu)-DME, is mainly associated with changes in the (formal) oxidation state of titanium between Ti2+ and Ti3+.Keywords: McMurry reaction; TiCl3(1,2-dimethoxyethane); Low valent titanium-ketone complexes

Base-free transfer hydrogenation of aryl-ketones, alkyl-ketones and alkenones catalyzed by an IrIIICp* complex bearing a triazenide ligand functionalized with pyrazole

An IrIIICp* complex (2) bearing a triazenide ligand functionalized with pyrazole was synthesized and fully characterized by spectroscopic methods and the structure confirmed by X-ray diffraction studies. The catalytic activity of 2 and the control complex 3, which lacks of pyrazole in its structure, was evaluated in the reduction of aryl-ketones, alkyl-ketones, α,β-unsaturated and γ,δ-unsaturated ketones. The catalytic system, using either 2 or 3, exhibited good to excellent selectivity when tested with ketones and alkenones at 90 °C in 2-propanol as hydrogen source under base-free conditions. Reactivity of 2 in 2-propanol and NaH gave a neutral metal hydride (4) while in the absence of base gave two major cationic hydrides species (5 and 6).

“Inverse” Frustrated Lewis Pairs: An Inverse FLP Approach to the Catalytic Metal Free Hydrogenation of Ketones

For the first time have boron-containing weak Lewis acids been demonstrated to be active components of Frustrated Lewis Pair (FLP) catalysts in the hydrogenation of ketones to alcohols. Combining the organosuperbase (pyrr)3P=NtBu with the Lewis acid 9-(4-CF3-C6H4)-BBN generated an “inverse” FLP catalyst capable of hydrogenating a range of aliphatic and aromatic ketones including N-, O- and S-functionalized substrates and bio-mass derived ethyl levulinate. Initial computational and experimental studies indicate the mechanism of catalytic hydrogenation with “inverse” FLPs to be different from conventional FLP catalysts that contain strong Lewis acids such as B(C6F5)3.

Cobalt-catalyzed transfer hydrogenation of C=O and C=N bonds

An earth-abundant metal cobalt catalyst has been developed for the transfer hydrogenation of ketones, aldehydes, and imines under mild conditions. Experiments are described which provide insights into the mechanism of the transfer hydrogenation reaction. The Royal Society of Chemistry 2013.

Direct, metal-free synthesis of benzyl alcohols and deuterated benzyl alcohols from p-toluenesulfonylhydrazones using water as solvent

A novel library of diverse alcohols was synthesized by metal-free couplings of diazoalkanes derived from p-toluenesulfonylhydrazones to water under reflux and microwave conditions, in high yields. In addition, this protocol was successfully applied in the synthesis of deuterium-labeled alcohols using deuterium oxide. Georg Thieme Verlag Stuttgart New York.

Arene ruthenium complexes as versatile catalysts in water in both transfer hydrogenation of ketones and oxidation of alcohols. Selective deuterium labeling of rac-1-phenylethanol

The preparation of three series of arene Ru(II) half-sandwich compounds with the functional ligand 4,4′-dimethoxy-2,2′-bipyridine (dmobpy) is described. The new cationic derivatives have the general formula [(η6-arene)RuCl(κ2-N,N-dmobpy)]X (arene = benzene, X = Cl- ([1]Cl), BF4- ([1][BF 4]), TsO- ([1]TsO), PF6- ([1][PF6]); arene = p-cymene (p-cym), X = Cl- ([2]Cl), BF4- ([2][BF4]), TsO- ([2]TsO), PF6- ([2][PF6]); arene = 2-phenoxy-1-ethanol (phoxet), X = Cl- ([3]Cl), BF4- ([3][BF 4]), TsO- ([3]TsO), PF6- ([3][PF6])). The structures of [1]Cl, [1]TsO, [2]TsO, [2][BF 4], and [2][PF6] were determined by X-ray crystallography. All of the complexes except the PF6- salts were water-soluble, and they behaved as active catalysts in two different processes: the transfer hydrogenation of water-soluble and -insoluble ketones to the corresponding alcohols, using HCOONa as the hydrogen source at pH 4, and the oxidation of rac-1-phenylethanol to acetophenone with tBuOOH at pH 7, both in aqueous solution. For the transfer hydrogenation with p-cymene complexes the aqua, formato, and hydride species were detected by means of 1H NMR experiments in D2O. It was found that the cationic hydrido complex was [(η6-p-cymene)RuD(dmobpy)]+. The reversible and pH-dependent formation of the hydroxo derivative was also observed. When the catalytic transfer hydrogenation was performed in D 2O, the 1-phenylethanol obtained was selectively deuterated at the benzylic carbon. Mechanistic proposals are also included.

Pincer Ru and Os complexes as efficient catalysts for racemization and deuteration of alcohols

The pincer complexes [MX(CNN)(PP)] (M = Ru, Os; X = Cl, OTf; HCNN = 1-(6-arylpyridin-2-yl)methanamine; PP = diphosphine) have proven to efficiently catalyze both racemization and deuteration of alcohols in the presence of a base. Chiral alcohols have been racemized at 30-50 °C using 1 mol% of Ru or Os pincer complexes and 5 mol% of KOtBu in 2-propanol. Primary and secondary alcohols are efficiently deuterated at the α position, with respect to the OH group, using 2-propanol-d8 as solvent with Ru or Os pincer complexes and KOtBu at 30-50 °C. For secondary alcohols incorporation of deuterium at the β position has also been observed. In 2-propanol-d 8 the pincer complexes catalyze the simultaneous deuteration and racemization of (S)-1-phenylethanol, the two processes being strictly correlated. For both reactions much the same activity has been observed with the Ru and Os complexes. The pincer complexes display a superior activity with respect to the related compounds [MCl2(NN)(PP)] (NN = bidentate amine or pyridine ligand). The synthesis of the new complexes [MCl(CNN)(PP)] (M = Ru, 2, 4 and Os, 6, 7; PP = dppb, dppf) and [Ru(OTf)(CNN)(dppb)] (3) is also reported. The Royal Society of Chemistry 2011.

The epimetallation and carbonation of carbonyl and imino derivatives: Epivanadation route to 2-amino and 2-hydroxy acids

The feasibility of hydrocarboxylating carbonyl and imino derivatives by the two-step process of epimetallation and carbonation has been demonstrated with the model substrates of 9-fluorenone and 9-fluorenone anil. With lithium vanadium dihydride as the epimetallating agent, such hydrocarboxylation has led to a 75% yield of 9-hydroxy-9-fluorenecarboxylic acid and a 65% yield of 9-(N-phenylamino)-9-fluorenecarboxylic acid, respectively. Some initial success in extending the scope of this reaction to other substrates, such as benzophenone, has been achieved by using other epimetallating agents, like the presumed LiV(CH3)2 and Ti(OPri)2. A brief review of the processes and organic synthetic applications of epimetallation and transfer epimetallation of C-C π-bonds is offered as background.