32102-31-1

Upstream product

• 932-31-0 ortho-tolylmagnesium bromide 
• 98-86-2 acetophenone 
• 917-64-6 methyl magnesium iodide 
• 25187-00-2 2-iodobenzophenone 
• 131-58-8 2-Methylbenzophenone 
• 75-16-1 methylmagnesium bromide 
• 917-54-4 methyllithium 
• 74-88-4 methyl iodide 
• 577-16-2 2-Methylacetophenone 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 32102-33-3 Dimethyl-[2-(1-phenyl-1-o-tolyl-ethoxy)-ethyl]-amine 
• 1201847-17-7 C₂₂H₂₈O 
• 947-77-3 1-methyl-2-(1-phenylvinyl)benzene 
• 131-58-8 2-Methylbenzophenone 

Relevant academic research and scientific papers

Catalytic Enantioselective Addition of Aryl Grignard Reagents to Ketones

We report a catalytic system for the challenging enantioselective addition of aryl Grignard reagents to ketones. Using a simple, one-pot procedure under mild conditions, a wide range of aromatic ketones are converted into diaryl alcohols in good yields and with good enantioselectivities. The catalytic enantioselective addition of aryl Grignard reagents to ketones is now possible. Using a readily available Ar-BINMOL ligand and titanium(IV) isopropoxide in a simple, one-pot procedure under mild conditions, a wide range of aromatic ketones are converted into diaryl alcohols in good yields and with good enantioselectivities.

Highly enantioselective arylation of aldehydes and ketones using AlArEt2(THF) as aryl sources

A series of AlArEt2(THF) (Ar = Ph (la), 4-MeC6H 4 (1b), 4-MeOC6H 4 (1c), 4-Me 3SiC6H4 (1d), 2-naphthyl (le)) were synthesized from reactions of AlEt2Br(THF) with ArMgBr. In CDC13 solution, the 1H NMR spectra showed that AlArEt2(THF) compounds exist as a mixture of four species of formulas of AlAr xEt3-x (THF) (x = 0, 1, 2, or 3). AlArEt2(THF) compounds were found to be superior and atom-economic reagents for asymmetric aryl additions to organic carbonyls. Aryl additions of AlArEt2(THF) to aldehydes catalyzed by the titanium(IV) complex of (R)-H8-BINOL were efficient with a short reaction time of 1 h, affording aryl addition products as exclusive or main products in high yields and excellent enantioselectivities of up to 98% ee. Although ethyl additions to aldehydes occurred in minor extent, this study demonstrates that increasing the amount of AlArEt2(THF) from 1.2 to 1.4 or to 1.6 equiv significantly improved the aryl addition products of up to >99%. On the other hand, asymmetric arylations of AlArEt2(THF) to ketones employing a titanium(IV) catalyst of (S)-BINOL produced optically active tertiary alcohols exclusively in excellent enantioselectivities of up to 94% ee.

Gold(I)-catalyzed oxidative cleavage of a C-C double bond in water

Oxidative cleavage of the C=C bond to afford ketone or aldehyde products with tert-butyl hydrogenperoxide (TBHP) as the oxidant can be catalyzed by AuCl with neocuproine (1) in water.

C,O-dilithiated diarylmethanols: Easy and improved preparation by naphthalene-catalysed lithiation of diaryl ketones and reactivity toward electrophiles

The lithiation of different diaryl ketones 1 with an excess of lithium powder and a catalytic amount (8 mol %) of naphthalene in tetradrofuran at -30°C leads to the formation of the corresponding dianions of the type I, with Met=Li, which react with several electrophiles (E+=MeI, EtBr, Pr(i)CHO, PhCHO, cyclohexanone, MeCN) to give, after hydrolysis, the expected substituted diarylmethanols 2.

A New Ketyl Radical Probe. Dehalogenation of o-Halobenzophenone

The reactions of o-, m-, or p-bromobenzophenone and o-iodobenzophenone with various Grignard reagents were carried out in diethyl ether at 0 deg C.The product analysis showed that these halobenzophenones can be a good chemical probe to evaluate the electron-transfer ability of nucleophiles to the aromatic ketones.

Electron Transfer in Reactions of Ketones with Organolithium Reagents. A Carbon-14 Kinetic Isotope Effect Probe

Kinetic isotope effects have been determined for reactions of ketones labeled with carbon-14 at the carbonyl carbon with MeLi and Me2CuLi in diethyl ether at 0 deg C.Observed isotope effects were as follows: (C6H5)2C=O + MeLi, 12k/14k = 1.000 +/- 0.002; (C6H5)2C=O + Me2CuLi, 1.029 +/- 0.005; 2,4,6-Me3C6H2COC6H5 + MeLi, 1.023 +/- 0.004.The relative reactivities of ortho-, meta-, and para-substituted benzophenones with these reagents were also determined by the competition experiments.These results are consistent with an electron transfer step which is followed by a carbon-carbon bond-formimg step that is or is not rate determining depending on the structure of ketones and reagents.The reaction of benzophenone with MeLi proceeds via rate-determining electron transfer; the change in nucleophile from MeLi to Me2CuLi shifts the rate-determining step from electron-transfer to recombination; the change in ketone from benzophenone to 2,4,6-trimethylbenzophenone also shifts the rate-determining step from electron transfer to recombination because the latter step becomes slower for the more hindered ketone.The extent of the geometrical change of the substrate at the electron-transfer transition state of the reaction of benzophenone with MeLi was estimated to be small on the basis of the magnitude of the KIE and teh ρ value of the Hammett correlation.

NEW METHODOLOGY IN DETERMINING EVIDENCE FOR SINGLE ELECTRON TRANSFER IN THE REACTION OF GRIGNARD REAGENTS WITH KETONES

A new method is reported to determine the existence of single electron transfer in the reaction of Grignard reagents with ketones.The method involves the determination of pseudo-first order rate constants by following the rate of disappearance of the paramagnetic intermediate and relating the rate of this disappearance to the appearance of the product.The reactions of methyl-, phenyl- and t-butyl-Grignard reagents with substituted benzophenones were examined.This method should be applicable to a wide range of organometallic reactions.

Organometallic Reaction Mechanisms. 17. Nature of Alkyl Transfer in Reactions of Grignard Reagents with Ketones. Evidence for Radical Intermediates in the Formation of 1,2-Addition Product Involving Tertiary and Primary Grignard Reagents

When a Grignard reagent reacts with an aromatic ketone, a radical anion-radical cation pair is formed which can collapse to give 1,2-addition product or dissociate to form a radical anion and a free radical within the solvent cage which in turn can collapse to 1,2-addition product or a conjugate addition product or escape the solvent cage to form pinacol.The 1,2-addition products, which form after dissociation of the radical anion-radical cation pair, show free-radical character as indicated by the cyclized 1,2-addition products formed from the reaction of a tertiary Grignard reagent probe with benzophenone in THF and from the reaction of a primary Grignard reagent probe (neooctenyl Grignard reagent) with benzophenone in ether.The 1,6-addition products, which come about after dissociation of the radical anion-radical cation pair, show free-radical character as evidenced by the cyclized 1,6-addition products formed in all of the reactions which involve the tertiary probe Grignard reagent (in all solvents studied) with benzophenone and 2-MBP and also in the reaction of the neooctenyl probe Grignard reagent with 2-MBP.