22817-11-4

Upstream product

• 529-20-4 2-methylphenyl aldehyde 
• 6921-34-2 benzylmagnesium chloride 
• 100-39-0 benzyl bromide 
• 87100-28-5 pinacol benzylboronate 
• 122-78-1 phenylacetaldehyde 
• 96-09-3 styrene oxide 
• 16419-60-6 2-Methylphenylboronic acid 

Downstream Products

• 16216-13-0 2-phenyl-1-o-tolylethanone 
• 74942-20-4 2-bromo-2-phenyl-1-(o-tolyl)ethanone 
• 74942-21-5 2-amino-5-phenyl-4-(o-tolyl)thiazole 
• 74942-22-6 5-phenyl4-(o-tolyl)thiazole 
• 129448-69-7 1-(2-methylphenyl)-2-phenyl-3-(3-methoxyphenyl)-1-propanone 
• 799804-26-5 2-mesyloxy-1-(2-methylphenyl)-2-phenyl-ethanone 
• 16619-12-8 2-phenyl-indan-1-one 

Relevant academic research and scientific papers

Chemoselective Benzylation of Aldehydes Using Lewis Base Activated Boronate Nucleophiles

A benzylation of aldehydes using primary and secondary benzylboronic acid pinacol esters is reported. Activation of the boronic ester with s-butyllithium rendered it nucleophilic toward aldehydes. The activated nucleophile chemoselectively transfers the benzyl group over the sec-butyl group, providing excellent yields of the benzylated products. 11B NMR experiments were performed to study the mechanism of this transformation.

Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair

Highly enantioselective bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary alcohols in high yields with excellent enantioselectivities (up to 95% ee). The isolation of an α-silylcarbinol intermediate as well as DFT calculations revealed that the 1,2-anionotropic rearrangement occurred via a bisguanidinium silicate ion pair, which is the stereodetermining step. The chiral center formed is then retained without inversion through the subsequent [1,2]-Brook rearrangement. Crotyl acylsilanes were smoothly transformed into homoallylic linear crotyl alcohols with retention of E/Z geometry, and no branched alcohols were detected. This clearly suggested that the 1,2-anionotropic rearrangement occurred through a three-membered instead of a five-membered transition state.

Pd-Catalyzed Conjunctive Cross-Coupling between Grignard-Derived Boron “Ate” Complexes and C(sp2) Halides or Triflates: NaOTf as a Grignard Activator and Halide Scavenger

Catalytic enantioselective conjunctive cross-couplings that employ Grignard reagents are shown to furnish an array of nonracemic chiral organoboronic esters in an efficient and highly selective fashion. The utility of sodium triflate in facilitating this reaction is two-fold: it enables “ate” complex formation and overcomes catalytic inhibition by halide ions.

Synthetic method for diaryl-substituted ethanol compound serving as medical intermediate

The invention relates to a synthetic method for a diaryl-substituted ethanol compound serving as a medical intermediate shown as a formula (III). The method comprises the following steps: reacting a compound shown as a formula (I) and a compound shown as a formula (II) in a hermetic way in an organic solvent in the presence of a catalyst and an alkali; performing posttreatment at the end of the reaction to obtain a compound shown as the formula (III), wherein R1 and R2 are independently selected from H, alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms or halogen; or R2 and a benzene ring which is connected with the R2 form a naphthalene ring. According to the synthetic method, the diaryl-substituted ethanol compound can be obtained at a high yield through comprehensive selection and coordination of a specific reaction substrate, the catalyst, the alkali and the organic solvent, and has good application prospect and industrial production potential in the field of synthesis of medical intermediates.

Photochemical preparation of highly functionalized 1-indanones

A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-π* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo-[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements.

Torsionally and Hydrophobically Modified 2,3-Diarylindenes as Estrogen Receptor Ligands

2,3-Diarylindenes are ligands for the estrogen receptor which display intrinsic fluorescence.In order to optimize the receptor binding affinity of these compounds while preserving their desirable fluorescence properties, a series of torsionally modified analogues were prepared.A fluorine or methyl group was introduced on either of the two phenyl substituents ortho to their attachment site to the indene nucleus, in order to increase the out-of-plane twist of the appended rings.The analogues were prepared by the benzylation of appropriate deoxybenzoins, followed by Friedel-Crafts cyclic alkylation-dehydration.Comparison of the X-ray crystal structure of one analogue with unsubstituted analogues confirms the torsional perturbation effected by the ortho substituent.The torsional disposition of the C-2 aryl group in the substituted diphenylindenes is further investigated by UV (absorbance maxima and molar absorptivities), fluorescence (Stokes' shift), and NMR (chemical shifts).These spectroscopic measurements indicate increasing twisting between the C-2 aryl substituent and the indene system according to the following order: 3-ring o-Me-indene 9f diphenylindene 15 = 20 deg 3-ring o-F-indene 9c 1-Me-indene 16 2-ring o-F-indene 9b 2-ring o-Me-indene 9e = 63 deg.The binding affinity of these analogues to the estrogen receptor was evaluated by a competitive radiometric receptor binding assay.While o-fluoro or o-methyl substitution on the 3-ring increases binding only slightly, binding of the o-fluoro 2-ring analogue is increased ca. 6-fold and the o-methyl analogue 11-fold, giving, in the latter case, a compound with an affinity equivalent to that of estradiol.The increase in binding affinity afforded by ortho substitution correlates with the increase in the torsion angle of the C-2 aryl ring.A thermodynamic evaluation of the receptor fit (Andrews, P.R.; Craik, D.J.; Martin, J.L.J.Med.Chem. 1984, 27, 1648) indicates that, for the o-methyl-2-ring analogue, the effect of the ortho substitution on increasing receptor binding appears to be a combination of increased surface area due to the substituent itself, together with a change in surface area of the ligand that results from the increased torsion of the two aryl rings.An o-fluoro substituent on the 2-ring provides a compromise between the relative planarity required for high fluorescence intensity and the molecular shape needed for increased estrogen receptor binding affinity. o-Methyl, o-fluoro, and p-methyl substitution of the 3-ring have no value in the development of a fluorescent, higher affinity 2,3-diarylindene.