54537-57-4

Upstream product

• 69352-05-2 2-(2-iodophenyl)propan-2-ol 
• 536-74-3 phenylacetylene 
• 7073-69-0 2-(2-bromophenyl)propanol 
• 1689-09-4 3,3-Dimethyl-3H-isobenzofuran-1-one 
• 1589-82-8 phenylmagnesium bromide 

Relevant academic research and scientific papers

Time and Temperature Dependent Palladium-Catalyzed Stereo- A nd Regioselective Alkoxy-arylation of Triple Bonds: Synthesis of (E)/(Z)-1,1-Disubstituted-3-(1-Phenylalkylidene)-1,3-dihydroisobenzofurans

The development of synthetic strategies enabling the stereo- A nd regio-selective synthesis of organic molecules is indispensable in the pharmaceutical industry. This work describes a stereo- A nd regioselective synthesis of (E)/(Z)-1,1-disubstituted-3-(1-arylalkylidene)-1,3-dihydroisobenzofurans catalyzed by palladium. The DHIBFs are achieved from readily available aryl bromides and ortho-alkyne tertiary alcohols via intermolecular aryl Heck coupling and intramolecular oxo-cyclization of the suitably situated hydroxyl group. Significantly, it was demonstrated that a Z-isomer was formed as a substantial isomer at 80 °C for 6 h, whereas the stable E-isomer was the predominant one at slightly vigorous conditions (100 °C for 12 h). In addition, careful observation has also led to the realization that this double isomerization from Z-to E-isomer was triggered in the NMR tube itself in CDCl3 at room temperature. Significantly, this protocol, for the first time, enabled the synthesis of heavily substituted dihydroisobenzofurans, especially, bearing a tetra-substituted double bond.

Oxidative Kinetic Resolution of Cyclic Benzylic Ethers

A manganese-catalyzed oxidative kinetic resolution of cyclic benzylic ethers through asymmetric C(sp3)?H oxidation is reported. The practical approach is applicable to a wide range of 1,3-dihydroisobenzofurans bearing diverse functional groups and substituent patterns at the α position with extremely efficient enantiodiscrimination. The generality of the strategy was further demonstrated by efficient oxidative kinetic resolution of another type of five-membered cyclic benzylic ether, 2,3-dihydrobenzofurans, and six-membered 6H-benzo[c]chromenes. Direct late-stage oxidative kinetic resolution of bioactive molecules that are otherwise difficult to access was further explored.

Efficient copper-catalyzed cross-coupling reaction of alkynes with aryl iodides

A copper-catalyzed cross-coupling reaction of alkynes with aryl iodides is described. The system, tolerates a broad range of functional groups and enables the use of sterically demanding substrates with only 1.0-2.5 mol-% of Cu 2O and 1.0-2.5 mol-% of xantphos as the catalyst.

Ring-chain tautomerism as a factor in the reaction between Grignard reagents and substituted phthalides

With phthalide two equivalents of Grignard reagent react rapidly in a reaction which could not be controlled to give stepwise addition. In contrast, 3,3- and 4,7-disubstituted phthalides react with only one equivalent of organometallic reagent. The primary addition product formed from one equivalent each of phthalide and Grignard reagent exists in a ring-chain tautomerism whose position is controlled by the interaction between the substituents present in the phthalide and the alkyl group introduced by the Grignard reagent. With substituted phthalides, ring opening of the primary addition product is prevented by these interactions and thus a second equivalent of Grignard reagent does not react. In the absence of substituents, ring opening and the reaction of a second equivalent occurs. Somewhat related effects appear to exist in the reaction between Grignard reagents and phthalic anhydride and in the dehydration of substituted phthalyl alcohols to their corresponding phthalans.