67031-12-3

Upstream product

• 127590-13-0 1-Phenyl-2-(trimethylsiloxy)cyclopropancarbonsaeure-methylester (trans) 
• 103-82-2 phenylacetic acid 
• 201230-82-2 carbon monoxide 
• 1865-29-8 2-phenyl-acrylic acid methyl ester 
• 22979-35-7 Methyl phenyldiazoacetate 
• 536-74-3 phenylacetylene 
• 186581-53-3 diazomethane 
• 137386-82-4 trans-3,3-difluoro-2-phenyl-1-cyclopropylcarboxaldehyde 
• 14815-73-7 methyl allylphenylacetate 

Downstream Products

• 105074-27-9 6,6-Difluoro-5-iodo-3-phenyl-tetrahydro-pyran-2-one 
• 105074-24-6 5,5-Difluoro-2-phenyl-pent-4-enoic acid 
• 121756-29-4 cis-5-allyl-4,5-dihydro-3-phenyl-2(3H)-furanone 
• 121756-28-3 trans-5-allyl-4,5-dihydro-3-phenyl-2(3H)-furanone 
• 74457-58-2 4-oxo-2-phenyl-butyric acid 
• 54897-85-7 4-methoxy-4-oxo-3-phenylbutanoic acid 
• 67030-91-5 3-Phenyl-5-brom-5-hydroxy-2(5H)-furanon 

Relevant academic research and scientific papers

TETRAHYDRO-IMIDAZO QUINOLINE COMPOSITIONS AS CBP/P300 INHIBITORS

The present disclosure is directed to inhibitors of the CBP/p300 family of bromodomains. The compounds can be useful in the treatment of disease or disorders associated with the inhibition of the CBP/p300 family of bromodomains. For instance, the disclosure is concerned with compounds and compositions for inhibition of the CBP/p300 family of bromodomains, methods of treating, preventing, or ameliorating diseases or disorders associated with the inhibition of CBP/p300 family of bromodomains, and methods of synthesis of these compounds.

Catalytic Enantio- And Diastereoselective Cyclopropanation of 2-Azadienes for the Synthesis of Aminocyclopropanes Bearing Quaternary Carbon Stereogenic Centers

We report the catalytic enantio- and diastereoselective preparation of aminocyclopropanes by the cyclopropanation of terminal and (Z)-internal 2-azadienes with donor/acceptor carbenes derived from α-diazoesters. The resulting cyclopropanes bear quaternary carbon stereogenic centers vicinal to the amino-substituted carbon and are formed as a single diastereomer in up to 99:1 er and 97% yield with 0.5 mol % of Rh2(DOSP)4 and only 1.5 equiv of the diazo reagent. Transformations with internal azadienes afford cyclopropanes with three contiguous stereogenic centers.

α-Tetrasubstituted Aldehydes through Electronic and Strain-Controlled Branch-Selective Stereoselective Hydroformylation

Hydroformylation utilizes dihydrogen, carbon monoxide, and a catalyst to transform alkenes into aldehydes. This work applies chiral bisdiazaphospholane (BDP)- and bisphospholanoethane-ligated rhodium complexes to the hydroformylation of a variety of alkenes to produce chiral tetrasubstituted aldehydes. 1,1′-Disubstituted acrylates bearing electron-withdrawing substituents undergo hydroformylation under mild conditions (1 mol % of catalyst/BDP ligand, 150 psig gas, 60 °C) with high conversions and yields of tetrasubstituted aldehydes (e.g., 13:1 regioselectivity, 85% ee, and 99% regioselectivity and >19:1 diastereoselectivity to tetrasubstituted aldehydes at rates >50 catalyst turnovers/hour. NMR studies of the noncatalytic reaction of HRh(BDP)(CO)2 with methyl 1-fluoroacrylate enable interception of tertiary alkylrhodium intermediates, demonstrating migratory insertion to acyl species is slower than formation of secondary and primary alkylrhodium intermediates. Overall, these investigations reveal how the interplay of sterics, electronics, and ring strain are harnessed to provide access to valuable α-tetrasubstituted aldehyde synthetic building blocks by promoting branched-selective hydroformylation.

Enantiomerically pure bis(phosphanyl)carbaborane(12) compounds

Enantiomerically pure (RP,RP)- and (R P,SP)-1,2-bis[1-adamantyloxy-( - )-menthyloxyphosphanyl]- closo-dicarbaborane(12), 1,2-bis[bis( - )-menthyloxyphosphanyl]-closo- dicarbaborane(12) and 1,2-bis [bis (4-tert-butylphenyloxy)phosphanyl] -closo-dicarbaborane(12) were synthesised by the reaction of dilithiated l,2-dicarba-closo-dodecaborane(12) with two equivalents of the corresponding chlorophosphite. The phosphonites are stable towards epimerisation, oxygen, and water. P...P through-space coupling was observed, and the 3JPP coupling constants were determined by spectral simulation and DFT calculations. Late transition-metal complexes with molybdenum, and rhodium, were prepared to study the coordination properties of the bis(phosphanyl)carbaborane(12) compounds. Catalytic properties of various rhodium complexes were investigated in homogeneous catalytic hydroformylation reactions with, various olefins.

Highly regioselective rhodium-catalysed hydroformylation of unsaturated Esters: The first practical method for quaternary selective carbonylation

Highly regioselective hydroformylation of unsaturated esters can be achieved when a highly reactive, ligand-modified, rhodium catalyst is employed near ambient temperatures (15-50°C) and pressures over 30 bar. The use of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane shows distinct advantages over other commonly applied phosphanes in terms of reaction rate, and regio- and chemoselectivity. Hydroformylation of a range 1,1-di- and 1,1,2-trisubstituted unsaturated esters yields quaternary aldehydes that are forbidden products according to Keulemans Rule. The aldehydes can be reductively aminated with molecular hydrogen to give β-amino acid esters in high yield. The overall green chemical process involves converting terminal alkynes into unusual β-amino acid esters with only water generated as an essential byproduct. This catalytic system has also been applied to the hydroformylation of simple 1,2-disubstitued unsaturated esters, which have been hydroformylated with excellent α-selectivity and good chemo-selectivity for the first time.

Phenylphosphatrioxa-adamantanes: Bulky, robust, electron-poor ligands that give very efficient rhodium(I) hydroformylation catalysts

The cage phosphines 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6- phosphaadamantane (1a) and 1,3,5,7-tetraethyl-6-phenyl-2,4,8,trioxa-6- pnosphaadamantane (1b) have been made by the acid catalysed addition of PhPH2 to the appropriate β-diketones; the acid used (HCl, H 3PO4 or H2SO4) and its concentration affect the rate and selectivity of these condensation reactions. Phosphines 1a and 1b react with [PdCl2(NCPh)2] to form complexes trans-[PdCl2(1a)2] (2a) and trans-[PdCl 2(1b)2] (2b) as mixtures of rac and meso diastereoisomers. The platinum(II) chemistry is more complicated and when 1a or 1b is added to [PtCl2(cod)], equilibrium mixtures of trans-[PtCl2L 2] and [Pt2Cl4L2] (L = 1a or 1b) are formed in CH2Cl2 solution. Meso/rac mixtures of trans-[MCl(CO)(1a)2] M = Ir (6a) or Rh (7a) are formed upon treatment of MCl3·nH2O with an excess of 1a and the anionic cobalt complex [NHEt3][CoCl3(1a)] (9) was isolated from the product formed by CoCl2·6H2O and 1a. The νCO values from the IR spectra of 6a and 7a suggest that 1a resembles a phosphonite in its bonding to Rh and Ir. Crystal structures of meso-2a, meso-2b, rac-6a and 9 are reported and in each case a small intracage C-P-C angle of ca. 94° is observed and this may partly explain the bonding characteristics of ligands 1a and 1b. The cone angles for 1a and 1b are similar and large (ca. 200°). Rhodium complexes of ligands 1a and 1b are hydroformylation catalysts with similarly high activity to catalysts derived from phosphites. The catalysts derived from 1a and 1b gave unusually low linear selectivity in the hydroformylation of hexenes. This feature has been further exploited in quaternary-selective hydroformylations of unsaturated esters; catalysts derived from 1a give better yields and regioselectivities than any previously reported catalyst. The Royal Society of Chemistry 2005.

Rhodium catalysed hydroformylation of unsaturated esters

Rhodium catalysed hydroformylation of unsaturated esters has been studied. A pronounced temperature dependence was observed on the regioselectivity and catalytic activity for these reactions, and under the appropriate conditions, it is possible to obtain preferentially either linear or quaternary products. A quaternary selective hydroformylation of methyl atropate to give 1,3-aldehydic esters has also been developed.

A Flexible Synthesis of Methyl 4-Oxobutanoates and Their Derivatives

Ring cleavage of several methyl 2-trimethylsiloxycyclopropanecarboxylates 3 provides rather sensitive methyl 4-oxobutanoates (β-formyl esters) 4 in excellent yields.Siloxycyclopropanes 3 are easily available either directly from the corresponding silyl en

RING OPENING REACTION OF gem-DIFLUOROCYCLOPROPYL KETONES WITH NUCLEOPHILES

Syntheses of gem-difluorocyclopropyl ketones (3a-d) and their reactions with nucleophiles are described.Ring opening reactions of 3a, c and d with a methanolate and a thiolate anion took entirely different courses of bond scission of the cyclopropane ring.